What Have We Learnt About Heavy Carbenes Through Laser Flash Photolysis Studies?

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INVITED ARTICLE www.rsc.org/pccp | Physical Chemistry Chemical Physics
What have we learnt about heavy carbenes through laser flash photolysis
studies?
Rosa Becerraa and Robin Walsh*b
Published on 14 March 2007. Downloaded by Universidad Autonoma de Nuevo Leon on 25/01/2017 13:36:07.
Received 7th December 2006, Accepted 26th January 2007

First published as an Advance Article on the web 14th March 2007
DOI: 10.1039/b617844h
Time resolved gas-phase kinetic studies have contributed a great deal of fundamental information
about the reactions and reactivity of heavy carbenes (silylenes, germylenes and stannylenes)
during the past two decades. In this article we trace the development of our understanding
through the mechanistic themes of intermediate complexes, third body assisted associations,
catalysed reactions, non-observed reactions and substituent eects. Ab initio (quantum chemical)
calculations have substantially assisted mechanistic interpretation and are discussed where
appropriate. Trends in reactivity are identified and some signposts to future studies are indicated.
This review, although detailed, is not comprehensive.
1. Introduction then we have extended our studies using this technique to the
detection and kinetic study of SiH2, SiD2, MeSiH, PhSiH,
Heavy carbenes are the molecules formed by the divalent ClSiH, GeH2, GeMe2, MeGeH and SnMe2. Our early work
states of silicon, germanium, tin and lead. They are of formula was summarised and reviewed by us8 (and Jasinski9) in 1995
MX2 where M is the metal (or metalloid) and X a ligand such and last year we published a joint review of our work on
as H, Me, or halogen. Their chemistry is of importance for germylenes and stannylenes largely carried out in collabora-
the breakdown processes of organometallic compounds of tion with the group of Egorov and Nefedov.10 These reviews
these elements and has practical significance in industrial were detailed and comprehensive and organised by reaction
applications involving chemical vapour deposition (CVD). type (insertion, addition and reaction with n-type lone pair
When we began our work in this area, there was already quite donors). We feel that there is now a need, not only for
a lot known of a general nature about the chemical structure updating the silylene part of this field, but to present the
of heavy carbenes (bent molecules with singlet ground states) results in a dierent way. The arrangement of material is
and patterns of reaction (insertion into ZH bonds (Z = other aimed to stress certain themes, which have emerged as char-
atom, often of a Group 14 element), addition to p-bonds, acteristic of the kinetics and mechanisms of the heavy car-
reactions with lone-pair donors).1 Some species, e.g. SnII benes. The review is not comprehensive, although we have
compounds suciently stabilised by large ligands, had even tried to include as many recent results as possible. However
been prepared and studied directly in solution.2 Information the review does also incorporate a number of findings of
about reactivity came from a variety of sources, but, apart quantum chemical (ab initio) calculations, which have pro-
from a few matrix-isolation experiments, was largely inferred vided useful insight into reaction mechanisms and served as an
from product analytical studies where heavy carbenes were increasingly valuable tool to complement the kinetic studies.
thought to be likely intermediates. The bulk of the information
pertained to silylenes, and rather little to germylenes, stanny-
lenes and plumbylenes. The first paper on a direct, time- 2. Background
resolved study of the prototype species, SiH2, was that of It is worth considering briefly some of the salient properties of
Inoue and Suzuki in 19853 who observed it by LIF (Laser heavy carbenes and the general nature of their reactions before
Induced Fluorescence) and reported several rate constants for delving into specific details of their kinetics and mechanisms.
its gas-phase reactions using laser flash photolysis. Stimulated
by this, Jasinski carried out and published the first detailed 2.1 Structure, bonding and stability
studies4 on SiH2 kinetics employing optical absorption, rather Symmetrical heavy carbene hydrides, heavy methylenes (SiH2,
than LIF, to monitor it. Around the same time, Strausz group
GeH2, SnH2), have C2v structures with 1A1 ground states and
were investigating the kinetics of SiCl2 reactions using con- 3
B1 excited states11 as shown in Fig. 1. They contrast with
ventional flash photolysis.5 Our interest in the kinetics of methylene, CH2, where 3B1 is the ground state and 1A1 the
silicon-containing species6 led us to follow shortly thereafter excited state.12 The heavy methylenes have the geometrical
with the first direct gas-phase kinetic studies of SiMe2.7 Since structures shown in Table 1. A simple discussion of the
bonding in SiH2, the prototype heavy carbene, was given in
a
Instituto Quimica-Fisica Rocasolano, CSIC, C/Serrano 119, 28006 our earlier review.8 A detailed and interesting discussion of the
Madrid, Spain dierences between the bonding and structures of CH2 and
b
School of Chemistry, University of Reading, Whiteknights, PO Box
224, Reading, UK RG6 6AD. E-mail: r.walsh@reading.ac.uk; SiH2 has recently been published by Apeloig, West and
Fax: +44 118 378 6331; Tel: +44 117 8456 colleagues.13 It is known, in particular for the silylenes,8 but
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Table 2 Some thermodynamic data for heavy methylenes
Species DHf1/kJ mol%1 DSSE/kJ mol%1 Ref.

SiH2 +273 & 2 93 & 3 8,16
GeH2 +237 & 12 119 & 20 14
SnH2 +243 & 5 111 & 8a 15
a
Called the inert pair eect in ref. 15.
Fig. 1 Orbital diagram for the two lowest states of silylene.
particular complexes influence the kinetic course of many of

also for the other heavy carbenes, that the valence shell s
the reactions studied.
electrons of the heavy (group 14) element are significantly
lower lying in energy than the p electrons which are largely 2.3 Energy release in heavy carbene reactions
involved in forming the bonds to the ligands. This gives rise to
The vast majority of heavy carbene reactions involve the
a stabilisation eect which we have called divalent state
creation of two bonds at the expense of one and therefore
stabilisation, the energy value (DSSE) for which is defined as
involve the release of considerable quantities of energy. This is
follows:
illustrated for some prototype reactions8,14,1623 for SiH2,
DSSEMX2 DX3 M-X % DX2 M-X GeH2 and SnH2 in Table 3. Energy release in these reactions
initially produces a vibrationally excited product. Depending
where D(X3M-X) and D(X2M-X) are the first and second on the magnitude of the energy release and the availability of
bond dissociation energies (enthalpies) of MX4. The further reaction pathways, this vibrationally excited species
values8,1416 of DHf1 and DSSE for MH2 are given in Table may react further or redissociate back to reactants. In the gas-
2. A fuller discussion of DSSE values for silylenes is given in phase these processes will be in competition with collisional
our earlier review.8 energy removal (stabilisation). This situation means that these
reactions can show characteristic pressure dependences of the
2.2 Nature of heavy carbene reaction processes rate constants, and many examples of this phenomenon are
now known. Such pressure dependences, characteristic of third
It is clear from Fig. 1 that (1A1) heavy carbenes have two
body assisted association reactions can be modelled by un-
potential sites of reactivity, viz an empty p orbital and a filled
imolecular rate theories such as RiceRamsperger
lone-pair orbital. Their reactions involve the use of both of
KasselMarcus theory (RRKM).24 This provides a useful
these orbitals. Since these reactions all involve acceptance of a
validation of reaction mechanism, and can be further used
lone pair (by the p orbital) and donation of a lone pair (from
to verify the value for the energy released in the reaction. This
the largely s2 orbital) on M which together create two new
is particularly useful, where such information is unreliable or
bonds (with the substrate) these processes may be considered
not available from other sources. This outcome is only possi-
examples of acid/base behaviour. More commonly the termi-
ble in gas-phase studies, since in solution solvent quenching of
nology electrophilic and nucleophilic has been used by prac-
the vibrationally excited product will eliminate any competi-
tioners in this field. These interactions are illustrated in Fig. 2
tion from other reaction channels.
for s bond insertion and p bond addition, two of the com-
monest reactions of heavy carbenes.
One of the significant developments in our understanding of 3. Method
these reactions, has been the finding, largely though theoretical
Laser flash photolysis has become a standard tool in the
calculations, that these processes do not occur simultaneously
arsenal of techniques available for detection and monitoring
but rather in stages, with the electrophilic interaction preced-
of transient intermediate species. Although the first detection
ing the nucleophilic (in the majority of cases). This leads to the
system3 employed LIF, generally laser absorption has been
intermediacy of transient weakly bound complexes in many of
most widely used. The acronym LRAFKS (laser resonance
the heavy carbene reactions. These ideas were foreshadowed
absorption flash kinetic spectroscopy) was proposed by
by the early kinetic studies on silylenes,8,9 which pointed to the
Jasinski.4 The particularly high reactivity of heavy carbenes,
involvement of these complexes for the interpretation of
results in terms of mechanism. This review illustrates how
Table 1 Geometries of the heavy methylenes (1A1 states)
MH2 RMH/A Bond angle/1

a
SiH2 1.514 92.0a
GeH2 1.588b 91.2b
SnH2 1.800c 89.7c
PbH2 1.851c 90.3c
a b
Experimental value, ref. 11a. Experimental value, ref. 11b.
c Fig. 2 Orbital interactions involved during the typical s bond
Theoretical value, ref. 11c.
insertion and p bond addition reactions of heavy carbenes.
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Table 3 Energy release for some prototype heavy carbene reactions
Reaction DH1/kJ mol%1 Ref.

SiH2 + SiH4 - Si2H6 %227 8,16
GeH2 + GeH4 - Ge2H6 %166 14
SnH2 + SnH4 - Sn2H6 %141 17
SiH2 + C2H4 - c-H2SiC2H4 %201 8,18

GeH2 + C2H4 - c-H2GeC2H4 %104 19
SnH2 + C2H4 - c-H2SnC2H4 %34a 20
SiH2 + H2O - H3SiOH %305 21

GeH2 + H2O - H3GeOH %171 22
SnH2 + H2O - H3SnOH %101 23
Fig. 3 Rovibrational spectrum of GeH2 taken from ref. 27.
a
DEo value from ab initio calculation (PBE/TZ2P level).
highly resolved spectra means that a narrow line optical probe

is required for their monitoring. This is provided by a single
especially SiH2, GeH2, imposes several requirements: (a) a mode (ring) dye laser which can be tuned to the appropiate
photochemical rapid heavy carbene creation source, (b) an transition (RQ0(J = 5) line of the A 1B1(0,2,0) X 1A1(0,0,0)
appropriate optical monitor (i.e. the absorption or emission vibronic transition at 17259.50 cm%1 for SiH2, or PQ1(J = 6)
spectrum of the transient needs to be known and a convenient line of the A 1B1(0,1,0) X 1A1(0,0,0) vibronic transition at
laser system available for its detection) and (c) a rapid 17111.31 cm%1 for GeH2). For SiD2 a strong line at 17387.07
response detection system (nanosecond time resolution) sui- cm%1, suitable for kinetic studies, was obtained from a point-
table for the time scale (microseconds) of transient signal by-point scan using laser flash photolysis of PhSiD3 as the
decays. Requirement (a) is generally met by the use of excimer transient source.28 To our knowledge this spectral transition
lasers with typically intense, nanosecond time scale, UV pulses has not been assigned. Other heavy carbenes have broader
in combination with a suitable UV absorbing molecular heavy band spectra most of which were first obtained by matrix
carbene precursor. Conventional UV flash lamp sources can isolation.29 The gaseous spectra are typically red-shifted re-
also be used for SiCl2, SiBr2, which are less reactive.5,25 lative to those of the matrix. In addition there are spectral red-
Another method for creating heavy carbenes is that of infrared shifts descending the group 14 for any particular type of
multiphoton decomposition (IRMPD),26 although this has not species e.g. MMe2. The gas phase spectra of SiMe2 and GeMe2
been much used in direct kinetic studies. are shown in Fig. 4. Table 4 contains a list of absorbing
regions for heavy carbenes which have been investigated in the
3.1 Photochemical sources
gas phase.4,5,7,28,3036 The broad band species (SiMe2, GeMe2,
For the heavy carbenes, MX2, these can all be summarised by PhSiH, MeSiH, MeGeH, ClSiH, SnMe2) place less demand on
eqn (1): the detection system, and an argon ion laser, with nine
available lines in the 450515 nm region, has proved to be a
RMX2 Y hn ! RY MX2 1
convenient optical probe. The visible region is particularly
Although the photolysis wavelength depends on the precursor, suited for heavy carbene monitoring because it is relatively
the 193 nm line of an ArF laser is overwhelmingly the usual
choice. The precursor molecules themselves include PhSiH3
(for SiH2), Me5Si2H (for SiMe2), Me5Ge2H (for GeMe2) and
SnMe4 (for SnMe2) but the general reaction shown in eqn (2)
has been widely used for silylenes, germylenes and stannylenes.
It is true to say that while photodissociation of these pre-

cursors is suciently rapid for their widespread use there is
still a dearth of knowledge about their excited states and
primary photochemistry.
3.2 Detection and monitoring

Heavy carbenes possess strong absorptions in the visible and
UV regions arising from electronic transitions of type 1B1
1
A1. In the case of the hydrides SiH2 (SiD2) and GeH2, these
are highly resolved into large manifolds of single rovibrational
lines. An example of a spectrum (GeH2)27 is shown in Fig. 3. Fig. 4 The visible absorption spectra of SiMe27 (( ( () and GeMe235
The narrow line width of ca. 0.05 cm%1 (FWHM) of these ().
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Table 4 Approximate absorption (monitoring) wavelengths for se-

lected heavy carbenes (1B1 1A1 band) in the gas-phase
Species Dl/nm lmax/nm Ref.

SiH2 500650 579.391 4
SiD2 500650 575.139 28
GeH2 510660 584.409 30
MeSiH 430520 ca. 493 31

PhSiH 460520 ca. 500 32
ClSiH 410480 457.9 33
MeGeH 465505 ca. 485 34
Fig. 6 Typical exponential time decay profile for simple heavy
SiMe2 390490 457.9 7 carbene reactions (GeH2 + C2D4).63
GeMe2 430520 479.0 35
SnMe2 460580 ca. 514.5 36
SiCl2 308328 317.4 5
tories is shown in Fig. 5. With modern fast response photo-
SiBr2 340400 362 5
diodes and electronic signal detection, amplification and
storage are relatively straightforward. The raw experimental
uncluttered by absorptions of most desirable substrate mole- result consists of the time evolution of the transient absorption
cules. The use of lasers as detectors oers the benefit of over a suitable time period (usually microseconds). Fig. 6
increasing sensitivity by increasing absorption path lengths shows an example. Signal-to-noise is improved by the accu-
in practice to well over 1 m by means of multipassing (using mulation of the traces from several photolysis runs (excimer
Whites optics).7 shots) using a transient digitizer. It is important to check that
such experimental repetition does not seriously perturb the
3.3 Apparatus
gaseous reaction mixtures during a series of photolysis shots.
A schematic diagram of the laser flash photolysis apparatus To avoid reactant depletion or product interference gaseous
and experimental set up for such experiments in our labora- flowing systems can be employed. However if materials are
costly or of limited availability a static reaction vessel can be
used provided the irradiated volume is a relatively small
proportion of the total (o5%). With shot repetition rates of
ca. 1 Hz, there is plenty of time for replenishment of the
reaction zone by diusion between photolysis laser pulses.
Under typical operating conditions, excimer laser pulses of ca.
6080 mJ can create transient concentrations in the reaction
zone of ca. 0.1%1.0 mTorr (ca. 1013 molecule cm%3) which give
detectable absorbances of ca. 0.05. Precise knowledge of the
heavy carbene concentrations is not usually required since the
decay kinetics are mostly pseudo-first order.
Gaseous reaction mixtures consist of a few mTorr of pre-
cursor (sucient to give a signal), an appropriate pressure of
reactive substrate (which can be from a few mTorr up to
several Torr, depending on reactivity) and an inert diluent gas.
The diluent serves two purposes. The first function is to
thermalize the products of laser photolysis so that the heavy
carbene is present with a (relaxed) Boltzmann energy distribu-
tion. Usually 5 Torr (and often less) are sucient for this
purpose. Polyatomic bath gases, such as SF6 which does not
interfere with the chemistry, are best for this. Secondly, the
inert diluent serves as a pressure control for reaction when the
overall kinetics are pressure dependent. In practice the max-
imum pressure has turned out to be ca. 100 Torr for many
studies although 1 atm has actually been achieved. Transient
signals appear to be significantly quenched at higher pressures
(although the reasons are not understood). At high pressures
care has to be taken to ensure complete mixing of reagents.
3.4 Data processing
Fig. 5 Schematic diagram of laser flash photolysis apparatus used to The extremely high reactivities of heavy carbenes mean that
study the kinetics of heavy carbene reactions. [Note: only the heavy even in the presence of only a few mTorr of substrates, signal
methylenes, SiH2 and GeH2 require the dye laser probe.] decay is usually dominated by bimolecular reaction with the

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substrate, viz:
MX2 substrate ! product 3
Under operating conditions, substrate concentrations are al-

ways greater than those of the transient heavy carbene. This
means that the MX2 decay kinetics are pseudo-first order with
a rate constant, kobs, linearly dependent on [substrate]. The

true second order rate constant is obtainable from studies of
this dependence. This is standard kinetic treatment, easily
programmable with microcomputers with standard error
packages. Occasionally (for example in the reactions of SiMe2
with ethers37) more complex kinetics arise and this can be
handled through alternative computer fitting routines or nu-
merical integration packages, for a hypothesised mechanistic
model. Fig. 7 shows a typical set of second-order plots.38
Fig. 7 Typical set of second order plots for heavy carbene reactions
4. Results and discussion (GeH2 + Me3SiH).38
The main findings of these studies are set out in this section.
The focus is on mechanistic interpretation and covers the Since step (1) is a loose association process, it has been
topics of intermediate complexes, pressure dependent reac- assumed that it will have at most a weak temperature depen-
tions, reactions with complex kinetics, unobserved reactions dence, i.e. that E1 is approximately zero. This suggests that the
and the eects of substituents and finishes with a brief major temperature dependence is associated with k%1/k2. The
summary of reactivity trends within the group. overall activation energy, Ea, depends on which is the rate
determining step. If it is step (1), k = k1 and Ea = E1. If it is
4.1 Intermediate complexes step (2), k = k1k2/k%1 and Ea = E1 + E2 % E%1. The tighter
4.1.1 The intermediate complex mechanism and reaction nature of the transition state of step (2) compared with (1)
eciencies. As can be seen from Fig. 7, the gradients of the means that A2 will always be much less than A%1 (a value for
second order plots, i.e. the rate constants, decrease with A2/A%1 of ca. 10%3 has been estimated in the case of the SiH
increasing temperature. This is a characteristic feature of the insertion reactions of SiMe249). This means that steps (%1) and
kinetics of many heavy carbene reactions. It means that the (2) can be competitive (i.e. k%1 E k2) even though E2 may be
reactions (generally) have negative activation energies. This is less than E%1. In this case the overall activation energy, Ea will
illustrated in Tables 5 and 6, containing the Arrhenius para- be negative. Obviously the magnitude of the negative activa-
meters for a variety of reactions of SiH216,18,3946 and tion energy will depend on the precise values of E1, E%1 and E2
GeH2.14,19,47,48 The values are discussed in more detail later and the extent to which step (2) is rate determining (values for
but the key point is that the negative activation energies led to Ea as highly negative as 17.3 kJ mol%1 have been obtained for
the idea that these reactions involve intermediate com- the reaction of MeSiH + Me3SiH31). At suciently low
plexes.8,31,49 w A brief outline of the kinetic treatment invol- temperatures, step (1) will be rate determining but as tempera-
ving such complexes is therefore given here. The general ture increases step (2) will take over. This means that for this
reaction of a heavy carbene with a reactive substrate may be mechanism, in principle, activation energies will change with
written as shown in Scheme 1: temperature, becoming more negative as temperature in-
creases. As yet this phenomenon has not been observed. A
schematic potential energy surface representing this mechan-
ism is shown in Fig. 8. While the values for the negative
Scheme 1
Step (1) is the encounter step leading to complex formation, Table 5 Comparison of Arrhenius parameters for selected SiH2
reactionsa
step (%1) is the redissociation of the complex and step (2)
involves the reorganisation of the complex to product (or Reaction Log(A/cm3 molecule%1 s%1) Ea/kJ mol%1 Ref.
products, via a dierent dissociation process). The observation
SiH2 + SiH4 %9.91 & 0.04 %2.1 & 0.2 16
of single-exponential decays in most cases, supports the as- SiH2 + GeH4 %9.88 & 0.02 %3.3 & 0.3 39
sumption of a steady-state population of intermediate com- SiH2 + C2H4 %9.97 & 0.03 %2.9 & 0.2 18
plexes. The phenomenological second order rate constant is SiH2 + C2H2 %9.99 & 0.03 %3.3 & 0.2 40
SiH2 + NO %9.97 & 0.18 %3.4 & 1.3 41
given by:
SiH2 + Me2CO %10.17 & 0.04 %4.5 & 0.3 42
SiH2 + N2O %12.09 & 0.04 %2.0 & 0.3 43
SiH2 + CO2 %11.89 & 0.13 +16.4 & 1.2 44
k k1 k2 =k%1 k2 k1 =1 k%1 =k2 SiH2 + HCl %11.51 & 0.06 %1.9 & 0.5 45
SiH2 + O2 %11.08 & 0.04 %1.6 & 0.3 46
w Small negative activation energies (r4 kJ mol%1) can be alterna- a
High pressure limiting values (for pressure dependent reactions).
tively explained by angular momentum conservation considerations.
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Table 6 Comparison of Arrhenius parameters for selected GeH2 Table 7 Comparison of Lennard-Jones collision eciencies at 298 K
reactionsa for selected SiH2 reactions
Reaction Log(A/cm3 molecule%1 s%1) Ea/kJ mol%1 Ref. Reaction ka,b ZLJa,c Eciency/%
GeH2 + SiH4 %11.73 & 0.06 %4.6 & 0.4 47 SiH2 + SiH4 4.60 4.60 100
GeH2 + GeH4 %11.17 & 0.02 %5.2 & 0.7 14 SiH2 + GeH4 3.06 4.14 74
GeH2 + C2H4 %10.61 & 0.08 %5.4 & 0.6 19 SiH2 + C2H4 3.5 4.92 71
GeH2 + C2H2 %10.94 & 0.05 %6.1 & 0.4 48 SiH2 + C2H2 4.0 4.90 82
a SiH2 + NO 4.6 3.68 Z 100
High pressure limiting values (for pressure dependent reactions).
SiH2 + Me2CO 4.2 5.54 76
SiH2 + N2O 0.019 4.12 0.46

SiH2 + CO2 o4.2 ) 10%5 4.10 o1.02 ) 10%3
activation energies of Tables 5 and 6 are not particularly high, SiH2 + HCl 0.0723 4.04 1.79
SiH2 + O2 0.164 3.55 4.6
and in early studies of SiH2 reactions the case for involvement
of intermediate complexes could be regarded as ambiguous,
a
High pressure limiting values; units, 10%10 cm3 molecule%1 s%1. b See
Table 5 for references. c See ref. 46 (Table 8) for data sources of
more recently with the advent of high level quantum chemical
parameters needed to evaluate ZLJ.
(ab initio and DFT) calculations the case for intermediate
complex involvement has become compelling in many cases.
This is considered in more detail in the next section.
A question that arises from this mechanistic model is what Table 8 Comparison of Lennard-Jones collision eciencies at 298 K
limits the reaction rate, if there is no positive energy barrier. for selected GeH2 reactions
Many of our studies of heavy carbene kinetics suggest that Reaction ka,b ZLJa,c Eciency/%
their reactions are occurring at collision controlled rates (at
room temperature). Tables 7 and 8 provide values of the GeH2 + SiH4 0.126 4.06 3.1
GeH2 + GeH4 0.550 3.32 16.6
collision eciencies of the reactions already cited (in Tables GeH2 + C2H4 2.1 4.40 48
5 and 6) based on a comparison of their room temperature rate GeH2 + C2H2 1.30 4.42 29
constants with the (theoretical) Lennard-Jones collision num- a
High pressure limiting values, units: 10%10 cm3 molecule%1 s%1. b See
bers.46,47,50 The selection of reactions of SiH2 in Table 7 Table 5 for references. c See ref. 47 (Table 7) and ref. 50 (Table 6) for
divides into two classes, viz. reactions with SiH4, GeH4, data sources of parameters needed to evaluate ZLJ.
C2H4, C2H2, NO and Me2CO which do occur with high
eciency, and reactions with CO2, N2O, HCl and O2 which
The quantitative support for these arguments is provided in
do not. What determines these eciencies? It is not a question
the next section.
of reaction type since both groups include formal insertions
and p-type additions. Rather we believe it is a question of the
secondary barrier. If this is low enough the complex rearranges 4.1.2 Examples of reactions occurring via intermediate com-
to products without hindrance (the ecient reaction group). If plexes. Some examples of the structures and energies calcu-
it is high and positive, the reaction then has a real activation lated for the intermediate complexes of silylene16,21,42,44,46,51
energy (CO2). However, it can be low and lie only just below and germylene14,19,47,48,52 z reactions using quantum chemical
the reaction threshold energy (HCl) in which case it will give methods are shown in Figs. 9 and 10 and Tables 9 and 10.
rise to a transition state which has a relatively tight structure Many of the complexes can exist in more than one conforma-
although no overall energy barriera so-called entropy tion, but in those cases only the most stable conformers are
bottleneck. The Arrhenius A factors are consistent with this shown here. Although some complexes can rearrange to
interpretation. Similar arguments will apply to the GeH2 products in a single step, others undergo series of further
reactions of Table 8, although here the range of examples reactions via quite complicated potential energy surfaces de-
considered (and studied) is less extensive. tails of which are not shown here. All of the complexes must
surmount an energy barrier, the secondary barrier referred to
in the previous section. The values of these energy barriers,
corresponding to the rearrangement transition states, TS2, for
the examples selected, are shown in Tables 9 and 10. Some of
the barriers are positive indicating reactions with positive
activation energies. If the value is too high the reaction will
be too slow to observe, even though an overall reaction may be
thermodynamically possible. Many of the values for TS2 (for
those reactions studied) are negative, indicating the possibility
of barrierless overall reactions in principle. The question then
arising is how high does the secondary barrier have to be to
influence the rate of reaction. Another way of putting this
z The GeH2( ( (C2H2 intermediate, although a p-complex, is actually

Fig. 8 Schematic potential energy surface for a typical heavy carbene also an activated complex (transition state). In this sense it diers from
reaction. the rest.

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Fig. 9 Examples of structures of intermediate complexes formed in selected reactions of SiH2 (from ab initio calculations). For simplicity bond
lengths and angles are omitted. For details see ref. 16, 21, 42, 44, 45 and 51.
question is to ask, how much below the reaction energy Table 9 Calculated quantum chemical (ab initio) energy valuesa for
threshold does TS2 have to lie, in order for it to have no eect selected complexesb of SiH2 and their rearrangement barriers (TS2)
on the reaction rate. This has been discussed in part in the Complex Energy TS2(Energy) Level Ref.
previous section. The key to this is the competition between
c c
steps (%1) and (2). If k2 4 k%1, then the secondary barrier will H2Si( ( (H( ( (SiH3 %48.1 %44.9 MP2/6-311G(d,p) 16
H2Si( ( (OQCMe2 %82.8 %48.0 G2 42
have little or no eect. To relate this argument to the ener- H2Si( ( (OQCQO %12.2d +11.7 G2 44
getics requires a knowledge of A2/A%1. Although, in principle, H2Si( ( (OH2 %56 +16 G3 21
this will vary from reaction to reaction an approximate value H2Si( ( (ClH %22.5 %2.9 G3 45
H2Si( ( (N2 %26 +58 G3 51
is 10%3.31,49 Assuming Arrhenius form for these rate constants,
a
this means that the secondary barrier will have an eect H1(298 K) values relative to separated reactant species. b For details
provided E%1 % E2 o 3RTln10. The practicable range for of other complexes see text and/or related references. c Corrected for
zpve and thermal energy from Eel. d Anti form.
kinetic measurements is 300600 K and so this translates into
values of 17 kJ mol%1 (300 K) and 34 kJ mol%1 (600 K). Thus if
the energy (enthalpy) of TS2 is less than 34 kJ mol%1 below the perature. All these examples fit well with observations of their
threshold, there should be some eect of the secondary barrier eciencies (Tables 7 and 8). For the reactions SiH2 + CO2,
at least at the highest temperature of study. This value serves SiH2 + H2O, SiH2 + N2 and GeH2 + H2, TS2 is positive and
as a useful guideline, even though it is an approximation. If we so the reactions should either have positive activation energies,
examine the data of Tables 9 and 10, TS2 values for the or not go at all. This is true for three of these examples, but for
reactions, SiH2 + SiH4, SiH2 + Me2CO and GeH2 + C2H4 the fourth, SiH2 + H2O, reaction does occur. This exception is
lie at more than 34 kJ mol%1 below threshold and so this tells because the complex itself, H2Si( ( (OH2 is actually the end
us that secondary barriers should not inhibit these reactions. product of reaction. It lies in a suciently deep well with no
For the reactions SiH2 + HCl, GeH2 + C2H2, GeH2 + GeH4 low energy exit channel, that the reaction is a single step
and GeH2 + SiH4, TS2 values lie less than 34 kJ mol%1 below (although reversible) process. This reaction is discussed further
threshold, and so the secondary barriers may be expected to below, and there is reason to believe that if the complex could
reduce the eciencies of these reactions. For three of these be stabilised (by pressure), it would show high collision
reactions TS2 is less than 17 kJ mol%1 below threshold and so eciency. Some examples of potential energy surfaces are
the reaction eciency should be aected even at room tem- shown in Fig. 11 to illustrate the variety of situations.
These quantum chemical calculations are now suciently
reliable and extensive for us to believe that there is a high
Table 10 Calculated quantum chemical (ab initio) energy valuesa for

selected complexesb of GeH2 and their rearrangement barriers (TS2)
Complex Energy TS2(Energy) Level Ref.

H2Ge( ( (H2 %9 +50 QCISD(T) 52
H2Ge( ( (H( ( (GeH3 %14.4c %9.6c G2/MP2 14
H2Ge( ( (H( ( (SiH3 %28.4 %9.0 G2/MP2 47
H2Ge( ( (C2H4 %69 %68 G2/QCISD 19
H2Ge( ( (C2H2d %29 %29 G2/QCISD 48
a
H1(298 K) values relative to separated reactant species. b For details
Fig. 10 Examples of structures of intermediate complexes formed in
of other complexes see text and/or related references. c Corrected for
selected reactions of GeH2 (from ab initio calculations). For simplicity
zpve and thermal energy from Eel. d This is an activated complex
bond lengths and angles are omitted. For details see ref. 14, 19, 47, 48
(transition state).
and 52.
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Fig. 11 Some examples of calculated potential energy surfaces found for reactions of SiH2 and GeH2. The numbers are values of H1298/kJ mol%1.
For details see refs 14, 16, 44 and 45.
Fig. 12 Schematic association potential energy surface for some

typical heavy carbene reactions.
correlation between the calculated height of the secondary

barrier for reaction of the intermediate complex and the
measured collisional eciency of reaction. Not all the exam-
ples of Tables 7 and 8, have been the subject of theoretical
calculation, but in all cases where such calculations have been
carried out, there is consistency. Interestingly for SiH2 +
C2H4, where the reaction product is silirane,18 no intermediate
complex (p-complex) could be found by ab initio calculations
at the MP2 level.53
Fig. 13 Typical set of pressure dependent rate constants of a heavy

4.2 Pressure dependent reactions carbene association reaction. The data points are for reaction of
SiH2 + CH3CHO54 and the lines are RRKM fits.
4.2.1 Modelling. As indicated earlier, many heavy carbene
reactions give rise to pressure dependent rate constants in the
gas-phase. This arises because reactions are exothermic and increased. Such behaviour can be readily modelled using
the products are suciently vibrationally excited upon forma- RRKM theory,24 provided it is known that the reaction is
tion that they are only incompletely stabilised under the reversible without any side channels. In this case the calcula-
conditions of study. The mechanism and energy surface are tion simply becomes that for the reverse unimolecular decom-
shown schematically in Fig. 12. This is the reaction category position of the heavy carbene association product (Scheme 2).
known as third body assisted associations. The phenomenon
can be illustrated by the series of pressure dependent rate
constants shown in Fig. 13 for the reaction of SiH2 +
CH3CHO54 at five temperatures in the range 297599 K. This Scheme 2
set of curves illustrates the typical behaviour found in such
reaction systems with rate constant fall-o increasing as the
pressure is reduced at a given temperature, and the extent of While simple reversibility seems to hold for many heavy
fall-o (at a given pressure) increasing as the temperature is carbene reactions, some reactions have additional channels,

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and in these latter cases modelling can only be undertaken

with diculty.y
In the most favourable cases, e.g. SiH2 + SiH4,16 all the
parameters necessary for RRKM modelling are available and
the only uncertainty lies in the collisional stabilisation model.
Stepladder models have generally been used on the grounds
that they are most appropriate for the relatively large collider
gas partner, SF6, employed in most of the studies reviewed
here. The energy removal parameter, hDEidown, which best fits
the data in cases where it can be determined with reasonable
confidence,8,16,18 has values which lie in the range 9.612.0 kJ
mol%1 (8001200 cm%1). In a number of the pressure depen-
dent reactions studied, where there were other sources of
uncertainty, a value in this range was simply assumed. This
is not likely to be a major source of error. For the RRKM
modelling itself, it is by now well known24 that the key
quantities are the A factor and the critical energy, Eo, for
decomposition. In this short review, it is not appropriate to go
into elaborate detail over this. Suce to say that A factors,
Adiss, (used as the basis for wavenumber assignment of the
transition state vibrations) can usually be estimated with
reasonable confidence by combining the association A factor,
Aass, with the known or calculated reaction entropy, DS1,
using the microscopic reversibility relationship, ln(Aass/Adiss)
= DS1/R. This can often be done with sucient precision to
build variational character into the transition state, by means
of a temperature dependent A factor, although as yet, full Fig. 14 The eect of variation of Eo on RRKM calculated rate
Variational Transition State Theory56 has not been applied to constant pressure dependence curves for the reaction GeH2 + GeH414.
these reactions. It should be mentioned that whatever form of Eo values are in kJ mol%1.
Transition State Theory is used, the required A factor for
modelling must be the high pressure limiting value. In some
cases this can be obtained experimentally, in others some kind 4.2.2 Examples of pressure dependent association reactions.
of extrapolation is needed. This is a familiar problem in These are discussed here in terms of reaction type. The
unimolecular reaction modelling24 and has been solved in sequence of examples correlates roughly with increasing me-
most heavy carbene studies reviewed here, when extrapolation chanistic complexity and therefore illustrates the various cases
is not too lengthy, by a process of iteration in which AN (and which can arise in a reasonably logical way.
Eo) are initially assumed and then data fitting (at all available (a) Insertion reactions. The prototype reactions:
temperatures) is carried out and used to refine the initial
estimates of AN and Eo. SiH2 SiH4 ! Si2 H6 4
The most uncertain parameter in most calculations has
proved to be Eo, simply because the thermochemistry of heavy
carbene reactions (on which it depends) is generally poorly GeH2 GeH4 ! Ge2 H6 5
known. Two points may be made here. First, the expanding
use of quantum chemical (ab initio) calculations means that both exhibit pressure dependences which, when modelled, fit
theoretical values are becoming increasingly available. Sec- straightforwardly with simple single pathway product forma-
ondly, if all the parameters except Eo for an RRKM calculation over the full temperature ranges of study.16,14 z In the
tion are well enough known, then Eo may be determined, and case of reaction (4) the modelling is consistent with the known
used to improve our knowledge of the thermochemistry. This value for DHf1(SiH2) (Table 2). For reaction (5) the modelling
has been exploited in a number of cases. Fig. 14 shows an is used to obtain DHf1(GeH2) = +237 & 12 kJ mol%1 (also in
example of sensitivity of the fall o curves to Eo for the Table 2), which is reasonably close to other experimental and
decomposition of Ge2H6 formed in the reaction of GeH2 + theoretical values.14 This value is also quite close to that
GeH4.14 This was used to obtain a reasonable estimate for Eo (+233 & 12 kJ mol%1) obtained from modelling the pressure
and thereby DHf1(GeH2). Some specific examples of pressure dependence of reaction (6)47 viz
dependent reactions are discussed in the next section.
GeH2 SiH4 ! H3 GeSiH3 6
z In these reactions, and most others in this section unless explicitly

mentioned, the involvement of the weakly intermediate complexes,
y More sophisticated packages such as Multiwell55 are available for discussed in the previous section, has no eect on pressure depen-
such problems, but have not generally been applied yet in this area. dences, because populations of the complexes are generally too low.
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Interestingly, the fourth member of this set of reactions (7)39 either SiH2 or GeH2) with C2H4 and C2D4 is based upon the
viz occurrence of the rapid scrambling mechanism given below in
Scheme 3 (SiH2 case).
SiH2 GeH4 ! H3 GeSiH3 7
The key to this mechanism is the reversible nature of the
exhibits no pressure dependence. This is because the H3Ge- ring opening process producing ethylsilylene from silirane, the
SiH3 is formed chemically activated and has a fast, low energy silicon analog of reaction (10):
alternative exit channel to form GeH2 + SiH4. It is therefore

not reversible or subject to collisional stabilisation. The same 13
circumstances apply to SiH2 + Si2H6 (products SiH4 +
HSiSiH3) and SiH2 + Si3H8 (products SiH4 + Si(SiH3)2 or This process allows H and D to exchange and means that the
SiH4 + HSiSi2H5) which are similarly not pressure depen- vibrationally-excited siliranes (i.e. not collisionally stabilised)
dent.57 When the prototype reactions (4) and (5) are modified can redissociate to give SiHD and SiD2 as well as SiH2. Only
by alkyl substituents in the substrates, pressure dependences the regeneration of SiH2 can cause a pressure dependence. The
should be reduced, because the vibrational energy released in statistical probability of getting SiH2 is only 6.7% and so if the
the product is spread over a larger number of modes, making scrambling is complete, this is the maximum possible pressure
the lifetime longer, and collisional stabilisation more eective. dependence eect. A similar argument applies to the GeH2
This is supported by much reduced pressure dependences for case. Ab initio calculations of the potential surfaces, shown in
the reactions of SiH2 with the methylsilanes58 and GeH2 with Fig. 16, support these arguments, even though the relative
the ethylgermanes.59 stabilities of the 3-ring cycles and (ethyl) heavy carbene are
(b) Addition reactions. The prototype reactions: reversed between the silicon and germanium cases.
SiH2 C2 H4 ! product 8 For reactions of SiH2 with larger alkenes, viz propene and
isobutene, pressure dependences are less than for reaction (8),
GeH2 C2 H4 ! product 9 as expected for the formation of bulkier siliranes.64 What was
less expected is the finding, from the RRKM modelling, that
are both pressure dependent but dier mechanistically from strain energies of the siliranes increase with increasing methyl
one another.18,19 For reaction (8) the product is silirane substitution8. This contrasts with the cyclopropanes.65 The
(silacyclopropane) formed in a single step. RRKM modelling only reaction of GeH2 with a bulkier alkene for which kinetic
provides a good fit with Eo = 187 kJ mol%1 for silirane decom- data exist is that of GeH2 + C3H6 (propene).50 The pressure
position (reaction (%8)), corresponding to an overall DH1 dependence is less than that for the prototype GeH2 + C2H4,
value of %201 kJ mol%1.18 Theoretical (ab initio) calculations as expected, but Eo value of 105 kJ mol%1, required to fit the
give values for DH1 in the range %172 to %187 kJ mol%1 60,61 RRKM modelling, cannot be ascribed to the decomposition of
within the uncertainty of the modelling. The RRKM derived 2-methylgermirane (as in the original paper) because of the
value corresponds to DHf1(silirane) = +124 & 12 kJ mol%1 probable isomerisation:
and is the only experimentally based value currently available
for this quantity. For reaction (9) on the other hand, RRKM
modelling of the pressure dependence required an Eo value of 14
130 kJ mol%1 (for reaction (%9)), significantly higher than the
ab initio (G2) value of 95 kJ mol%1 for germirane decomposi-
tion.19 Not only that but the theoretical calculations of the
potential energy surface showed that germirane rearranges
with a low energy barrier to the more stable ethylgermylene,
viz
10
Although the data were not fitted quantitatively, it was clear

that a reasonable interpretation of the pressure dependence
was that C2H5GeH* was the species undergoing collisional
stabilisation even though germirane was the initially formed
product.19 The isotopic variants, of the prototype reactions,
SiH2 C2 D4 ! product 11 Scheme 3
GeH2 C2 D4 ! product 12
62,63
have also been studied and found to have hardly any
pressure dependence. The comparison between reactions with
8 This result was supported by the very low activation energy (130 kJ
deuterated and non deuterated ethylenes is shown in Fig. 15. mol%1) for hexamethylsilirane decomposition found by D. H. Berry
The explanation for striking dierences between reaction (of (unpublished results, see ref. 64).

Fig. 15 Comparison of rate constant pressure dependences of SiH2 and GeH2 with C2H4 and C2D4.
The prototype reactions with alkynes have also been studied, this.60e,66,67 For reaction (16) the situation is dierent. Ab
viz initio calculations suggest that germirene should isomerise
easily to HGeCHQCH2 (vinylgermylene) although not to
SiH2 C2 H2 ! product 15 H3GeCRCH (ethynylgermane). But HGeCHQCH2 pos-
sesses a low energy pathway to Ge(3P1) + C2H4. Although
GeH2 C2 H2 ! product 16 this involves an intersystem crossing, it is this latter pathway
which removes vibrationally excited HGeCHQCH2 and vir-
Reaction (15) shows a large pressure dependence while that of tually eliminates the pressure dependence. The analogous
(16) is very small.40,48 These are chemically even more com- pathway from HSiCHQCH2 to Si(3P1) + C2H4 is too
plicated processes than reactions (8) and (9) and readers are high in energy for it to aect the pressure dependence in
referred to the original articles for full details. RRKM calcula- reaction (15).67
tions show that formation of the 3-ring cycles, silirene and (c) Reactions with ketones/aldehydes. The following reac-
germirene alone is inadequate to explain the results. The tions have been investigated:42,54
pressure dependence and isotope studies for (15) suggest that
isomerisation pathways of silirene to both H3SiCRCH (ethy- SiH2 CH3 2 CO ! product 17
nylsilane) and HSiCHQCH2 (vinylsilylene) are occurring
under reaction conditions. Ab initio calculations support SiH2 CH3 CHO ! product 18
Fig. 16 Comparison of calculated potential energy surfaces for reactions of SiH2 and GeH2 with C2H4. The numbers are values of H1298/kJ mol%1
relative to threshold. For details see ref. 63.
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Although reactions (17) and (18) look as if they ought to be with the Eo values used by these authors to model the reactions:
just further examples of p-type additions, ab initio calcula-
SiH2 CD3 OD ! H2 Si ( ( ( ODCD3 20
tions42,54 indicate that the initial interactions are with the n
electrons of the O atom. Both reactions show significant
SiH2 CH3 2 O ! H2 Si ( ( ( OCH3 2 21
pressure dependences. RRKM modelling for each reaction,
carried out on the basis of siloxirane ring formation, could be The modelling of the observed pressure dependences of these
fitted to the data with an empirical Eo value.42,54 For both reactions, at four dierent temperatures for each, was used to
reactions ab initio calculations gave significantly lower Eo give kN values by extrapolation over several orders of magni-
values for the siloxiranes, indicating that this ring is less stable tude of pressure. The resulting values were well in excess of
than suggested by the RRKM calculations. However, the ab Lennard-Jones collision numbers and corresponded to the
initio calculations also suggested another pathway to the more following Arrhenius equations:
stable siloxyalkene product in both cases. It seems probable 3 %1 %1
logk1
20 =cm molecule s %7:6 & 0:2
that there are two competing reaction channels, as shown in
Scheme 4: % 7:7 & 0:6 kJ mol%1 =RT ln10
3 %1 %1
logk1
21 =cm molecule s %7:6 & 0:4
% 9:3 & 2:8 kJ mol%1 =RT ln10
The Arrhenius parameters are very unusual for SiH2 reactions,

having A factors some 2.5 powers of 10 higher than the highest
value for other SiH2 reactions (cf. Table 5), and positive
activation energies. The RRKM models are unusual in pre-
dicting rate constants which decrease with increasing tempera-
Scheme 4 ture at low pressures (as observed) but increase with
temperature at high pressures. We know of no other case like
The lack of a pressure dependent kinetic isotope eect in the this. The authors rationalise their findings by proposing a long
reaction, SiD2 + CH3CHO,54 rules out the occurrence of the range interaction between SiH2 and O-donor molecule in these
reversible isotope scrambling pathway via ethoxysilylene, viz. cases which gives rise to a centrifugal barrier which is unu-
sually high because of the weakly bound nature of the adducts.
While we cannot refute this argument, we have shown that in
the analogous reaction of SiH2 with water21,70 (reaction (22)
19 below), that such an explanation is unnecessary.
SiH2 H2 O ! H2 Si ( ( ( OH2 22
21
We have shown that it is perfectly possible to construct
This is consistent with the fact that the ab initio calculated RRKM models, consistent with ab initio calculations, which fit
barrier for this process is higher than that for the analogous the data for this reaction but do not give unusual values for the
silirane ring opening reaction (13). high pressure limiting rate constants (or their Arrhenius para-
(d) Reactions with alcohols, ethers and selected small mole- meters). In this last reaction we also found an unusual third
cules. These comprise a class of reactions where the products body eciency of H2O70 which is discussed in a later section.
are so weakly bound that they are hard to stabilise by Single temperature kinetic studies of GeH2 with D2O,
collisions. Many of them are close to the third order region CH3OH, CD3OD and CH3OCH3 show strong pressure de-
of pressure dependence and for all of them the high pressure pendences at 298 K.71 At a given pressure, rate constants are
limit of second order behaviour is well beyond practical less than those of their SiH2 counterparts,69 but no modelling
measurement. The consequence of this is that RRKM model- has been carried out.
ling is dicult, because AN and Eo are not known. The best The reaction of SiH2 + CO is another case72 where long
that can be done is to use estimates for AN and ab initio extrapolation is necessary to reach kN. RRKM modelling can
studies for Eo. For the reactions of SiH2 and GeH2 with be made to fit with ab initio calculations based on the process:
alcohols and ethers (and H2O), ab initio calculations have
SiH2 CO ! H2 Si ( ( ( CO 23
shown that, unlike in the other reactions so far considered, the
initially formed adduct (donoracceptor or zwitterionic com- One point of interest here is that the reaction is so slow that
plex), has a high barrier to further reaction.21,22,68,69 This rate constants could not be measured at partial pressures
means that eectively the adduct is the final product in the below 10 Torr of CO at 298 K. Despite this, the RRKM
gas-phase. Experimental evidence for the equilibrium forma- calculation suggested that at the high pressure limit the reac-
tion of these complexes has been obtained by Alexander tion occurs at the collision rate.
et al.68,69 and binding energies of 83 and 88 kJ mol%1 obtained The reaction of SiH2 + NO represents an even more
for H2Si( ( (O(D)CD3 and H2Si( ( (O(CH3)2, respectively. These complicated case.41 The pressure dependence curves show
are in reasonable agreement with ab initio calculations and also concave upwards curvature as can be seen in Fig. 17. High

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pressure limits are clearly not reached, and extrapolation was initio studies46,73 show that energy release is so great that any
impossible. However the data could be fitted to the reaction of singlet state intermediates will almost certainly fragment to
Scheme 5. product pairs, e.g. H2O + SiQO.
4.3 Reactions with complex kinetics

The large majority of kinetic studies of heavy carbenes con-
form to simple second order kinetics, albeit many of them with

pressure dependent rate constants. Departures from this in-
clude the reversible reactions of SiH2 with alcohols and ethers,
Scheme 5
mentioned in the previous section, and similar reactions of
SiMe2.37,74 An unusual phenomenon of a dierent kind was
In this scheme, at high pressures, the reaction product cyclo- found in our investigation of the SiH2 + H2O reaction.70
H2SiNO is stabilised by collisions (and formed at a collisional Initial measurements21 supported a third body assisted asso-
rate), whereas at low pressures, the vibrationally excited ciation process, as discussed above. However re-examination
intermediate (linear H2SiNO) isomerises and decomposes via of the system at low pressures (5 Torr added SF6) revealed an
a low energy competing channel. Ab initio calculations,41 SiH2 decay process with kobs showing a quadratic dependence
consistent with this interpretation, reveal an extremely com- upon [H2O] as shown in Fig. 18. We are not aware of any
plex potential energy surface leading to a number of possible similar kinetic behaviour in other gas-phase heavy carbene
final product combinations the most stable of which was reactions, although Leighs group has observed kinetics that
NH2 + SiQO. are second order in [ROH] for reactions between silenes and
The reaction of SiH2 with O2 is one with very little if any alcohols in solution.75 In this example, the data are consistent
pressure dependence. Our data46 suggests a slight lowering of with an H2O catalysed reaction of the initial adduct leading to
the rate constant at 1 Torr (SF6) at each of five temperatures in silanol as shown in Scheme 6. This mechanism is supported by
the range 297600 K while that of Guo et al.73 records no ab initio calculations.
dependence between 1.9 and 260 Torr (Ar) at 298 K. If there is This mechanism shows that the zwitterionic species formed
any pressure dependence, it is probably connected with colli- in the first step is readily converted into silanol by the second
sionally induced intersystem crossing in the H2SiOO adduct H2O molecule. Similar mechanisms can help to explain how
(the silicon analogue of the Criegee intermediate), because ab solution studies of silylene reactions with alcohols lead to the
OH insertion product, even though the calculated barrier to
isomerisation of the initial adduct is apparently too high.
A reaction where similar behaviour might be expected is
that of SiH2 + NH3. Our attempted investigation of that
system,76 however, revealed a fast reaction of SiH2, indepen-
dent of pressure, but dependent on laser intensity. Since NH3
absorbs the 193 nm radiation used to generate SiH2, it is highly
probable that the observed SiH2 kinetics are those of reaction
with NH2 radicals produced by NH3 photolysis. Another
system investigated by us77 where the kinetics were aected
by laser intensity was that of SiH2 + CH3Cl. Here the rate
constants gave rise to a curved Arrhenius plot. Since CH3Cl
also absorbs the 193 nm radiation it is likely that part of the
measured SiH2 decays is due to reaction with CH3 radicals
from CH3Cl photolysis. Ab initio calculations,77 however,
suggests a contribution to the rate from the abstraction
reaction (involving a donoracceptor intermediate complex):
SiH2 CH3 Cl ! CH3 ClSiH2 24
The calculations show that direct insertion of SiH2 into the

CCl has a prohibitively high barrier (103 kJ mol%1). This
supports the idea that, in general, silylene reactions with alkyl
chlorides proceed via an abstraction-recombination rather
than an insertion mechanism. A general conclusion here is
Fig. 17 Rate constant pressure dependences for the reaction

SiH2 + NO41. Scheme 6
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Table 11 Rate constant and activation energy limits for some non
observed reactions of SiH2 and GeH2
Reaction T/K k/cm3 molecule%1 s%1 Ea/kJ mol%1 Ref.

SiH2 + CH4 300 o3.9 ) 10 %15
423 78
610 o1.3 ) 10%15 445 78
SiH2 + SiMe4 296 o1.7 ) 10%13 416 78

527 o5.9 ) 10%13 423 78
SiH2 + N2 296 o3.0 ) 10%15 429 51

417 o3.8 ) 10%15 439 51
484 o2.6 ) 10%15 447 51
GeH2 + D2 293 o1.0 ) 10%14 411 52

585 o1.7 ) 10%14 419 52
barrier prohibits observation of this intermolecular reaction,

Fig. 18 Dependence of SiH2 decay constants on partial pressure of its intramolecular counterpart occurs readily as in, for exam-
H2O at fixed SF6 pressure (5 Torr) in the reaction SiH2 + H2O70. ple, the ring closure reaction of ethylsilylene to silirane, the
reverse of reaction (13). Lack of reaction of SiH2 with SiMe4
that if the substrate absorbs at the photolysis wavelength, it is confirms that SiH2 does not insert into SiC bonds any more
likely to cause kinetic complications. than into CH bonds. We are not aware of any calculations or
estimates of the barriers in this case.
In view of its anity for electronegative elements,81 and the
4.4 Unobserved reactions (reactions with positive activation fact that SiH2 reacts with CO and CO2, we had hoped to
energies) observe a reaction with N2.51 Ab initio calculations (G3 level)
Given the high eciencies of many heavy carbene reactions, however show that, apart from the existence of a weakly
arising from their highly electrophilic nature, it almost comes bound complex (see Fig. 9), all other plausible products are
as a surprise to find examples of reactions where reaction is not endothermic.51 The lack of reaction is therefore apparently
observed at all. It is true that part of the reason for ineciency explained, although it is not obvious to us why Si binds
may be a third body stabilisation requirement for some significantly less well to double bonded than to single bonded
reactions e.g. SiH2 + H2O, SiH2 + CO but there is good N in siliconnitrogen compounds. The complex (the silicon
reason to believe that in these cases, they should be highly analogue of diazomethane) is too weakly bound to be detect-
ecient at the high pressure limit. This has already been able in gas phase experiments, although its existence should be
discussed. But there are some reactions where quite large demonstrable in a matrix.
activation barriers exist. Experimental investigations in our The reaction of GeH2 with H2 is significantly exothermic,
laboratories have enabled us to set upper limits for the rate but is inhibited by the insertion barrier. Ab initio calculations
constants of some of these reactions51,52,78 which are listed in give values of +50 kJ mol%1 (QCISD level) and +48 kJ mol%1
Table 11. Also shown are lower limits for activation energies (B3LYP level).52 This contrasts with values of +5 and %2 kJ
calculated on the basis of estimated A factors. In order to mol%1 found by the same methods respectively for SiH2 + H2.
explore such limits, it was necessary to use ultra pure reagents, It appears that the longer GeH bonds in the transition state
because of the high risk of reaction of SiH2 or GeH2 with (compared with the SiH bonds in the Si analogue reaction)
impurities at the collision rate. The numbers give an idea of the require a greater extension of the HH bond to get sucient
measurement limits for laser flash photolysis studies of heavy orbital overlap. This causes the transition state to be strained,
carbenes. The only reaction with a significant barrier (16.4 kJ and makes understandable the lack of reactivity of GeH2 with
mol%1) for which we have real data is that of SiH2 + CO2,44 H2** compared with SiH2 + H2.8,9,82
listed in Table 5. The other reactions in Table 11, although not
observed, do reveal useful insights into the reactivity of SiH2 4.5 Substituent eects and comparisons of reactivity
and GeH2.
A high barrier for SiH2 + CH4 is confirmed by a thermo- Up to now this review has been largely about the heavy
chemical estimate of +59 & 12 kJ mol%1 based on the methylenes, SiH2 and GeH2, but in this section we highlight
measured activation energy of the reverse decomposition of some of the kinetic results obtained for substituted silylenes
CH3SiH3.79 Ab initio studies60e,80 give values of ca. +92 kJ and germylenes and also SnMe2. The key questions here are:
mol%1. Despite the unresolved dierence in values this never- (a) to what extent do substituents modify the behaviour of
theless shows that SiH2 has diculty inserting into CH MH2? and (b) how does the reactivity vary down the group
bonds, a fact well known to silicon chemists1. We have argued (i.e. from Si to Ge to Sn) for a particular substituted heavy
that part of the reason for this diculty is the polarity of the carbene?
Cd%Hd+ bond, which hinders the approach of the positively
** D2 was used in the actual experiments,52 to avoid the risk of non-
charged Si atom in SiH28,78 although there are undoubtedly observation of reaction for pressure dependence (third body stabilisa-
other factors. It should be noted however that, whereas the tion) reasons.

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Table 12 Some relative rate constants for SiH insertion reactions of Table 14 Some relative rate constants for SiH addition reactions of
SiH2 compared with those of other silylenes at 298 K SiH2 compared with those of other silylenes at 298 K and 10 Torr
(SF6)
krela
krela
Molecule MeSiHb PhSiHc SiMe2d ClSiHe
Molecule ClSiHb SiCl2c SiMe2
SiH4 5.6 7.8 2300 87 000
MeSiH3 2.0 1.05 215 1290 C2H4 3.2 1220 6.3d

Me2SiH2 2.1 1.7 64 245 C2H2 2.3 4500 6.9e
Me3SiH 0.90 0.65 57 144 a
krel = k(SiH2 + substrate)/k(SiXY + substrate): k(SiH2 + sub-
a
krel = k(SiH2 + substrate)/k(SiXY + substrate): k(SiH2 + substrate) values taken from ref. 18 (C2H4) and 40 (C2H2). b Based on
strate) values taken from ref. 16 (high pressure limit) and 58; see also data from ref. 33. c Based on data from ref. 5. d Based on data from
ref. 83. b Based on data from ref. 31. c Based on data from ref. ref. 64. e Based on data from ref. 86.
32. d Based on data from ref. 49. e Based on data from ref. 33
(assumed pressure independent).
SiMe285 and ClSiH33 insert more slowly into GeH bonds than
into SiH bonds. The rate constants on which this is based are
4.5.1 Substituent eects in silylenes and germylenes. Since given in Table 13. This result is counter-intuitive and appears
many reactions of SiH2 occur at the collision rate, it is hardly a impossible to explain with a direct mechanism, since the
surprise that substituents tend to reduce its reactivity. Table 12 expectation is that insertion rates will be fastest into the
shows a list of relative rate constants of SiH258,83 compared weaker bond and there is no doubt that GeH bonds are
with those of MeSiH,31 PhSiH,32 SiMe249 and ClSiH33 for the weaker than SiH bonds. This can only make sense in terms of
insertion reactions into the SiH bonds of the methylsilanes. the intermediate complex mechanism, where the secondary
Three points can be made about these numbers. First, some of barriers play an important role. The complexes with germane
the eects are quite large (approaching 105). Secondly, sub- substrates clearly only rearrange with more diculty than
stituent eects in the silylenes are not systematic (the second those with silane substrates.
methyl substituent has a much larger eect than the first). For addition reactions of silylenes the data on substituent
Thirdly, for a given silylene the relative rate constants diminish eects are less extensive. Some examples of comparison are
markedly with methyl substitution in the substrate. It is also shown in Table 14. There are no data for MeSiH but there are
notable that one Cl substituent outweighs the eect of two data for SiCl2. The eects of single Cl-for-H or double Me-for-
methyl groups. Unfortunately no data on these reactions exists H replacement produce relatively small rate constant reduc-
for SiCl2. We have argued8,33 that these numbers are consis- tions but double Cl-for-H substitution is significantly deacti-
tent with the intermediate complex mechanism and the eects vating. Because there are only limited pressure dependence
of secondary barriers, as discussed earlier. Alkyl, aryl or studies, these data can only easily be compared at 10 Torr
chloro substituents can all withdraw electrons inductively (SF6), but we doubt the picture will change greatly at the high
from the silylene. Aryl and chloro substituents can also donate pressure limits. The reason that addition reactions are less
electrons via p-interaction. If the latter is dominant these aected by substituents than insertion reactions may be due to
silylenes will be less electrophilic than silylene itself, and the lack of involvement of an intermediate complex.
therefore likely to form less strongly bound complexes. This While there are gas phase kinetic data for other reactions of
eect will tend to lower the rate constants. The electronic eect ClSiH33 and SiMe274,86 the scope for comparisons is small and
of alkyl substituents on silylene is not so clear, but less strongly therefore not included here. Interested readers are referred to
bound complexes also seem likely. By contrast, methyl groups the original papers. In hexane solution the rate constants for
in the substrate make the silicon more positively charged and SiPh2 are very close to those of SiMe2 for a variety of dierent
thereby lower the secondary barrier to rearrangement of the reactions,87 which is consistent with the more limited gas
complex. This eect will tend to raise the rate constants. These phase data for MeSiH and PhSiH (Table 12).
eects have been recently confirmed by ab initio calculations Although the data for substituted germylenes are more
for MeSiH58 and ClSiH.84 While this picture seems reasonable limited, the evidence so far suggests that the eects of sub-
and self consistent, it could still be argued that eects are not stituents are at least as dramatic as those for silylenes. Table 15
demanding of intermediate complexes. However we have shows a list of relative rate constants for GeH2 compared with
recently found the striking and unexpected result that both those of MeGeH34 and GeMe285,88 for the insertion reactions
Table 13 Some rate constant comparisons for SiH and GeH insertion reactions of SiMe2 and ClSiH at 298 K
kSiH/cm3 kGeH/kSiH/cm3
Reaction molecule1 s1 Reaction kGeH molecule1 s1
SiMe2 + Me2SiH2 5.5 ) 10%12 a SiMe2 + Me2GeH2 4.4 ) 10%13 b 0.080
ClSiH + MeSiH3 3.16 ) 10%13 c ClSiH + MeGeH3 6.61 ) 10%14 c 0.21
ClSiH + Me2SiH2 1.43 ) 10%12 c ClSiH + Me2GeH2 3.49 ) 10%13 c 0.24
a b
Ref. 58. Ref. 85. c Ref. 33
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Table 15 Some relative rate constants for GeH insertion reactions Table 16 Gas-phase rate constants for SnMe2 at 296 & 2 Ka
of GeH2 compared with those of other germylenes at 298 K
Substrate k/cm3 molecule%1 s%1
krela
1,3-C4H6 (5.97 & 0.17) ) 10%11
Molecule MeGeHb GeMe2 CH3CRCCH3 (7.84 & 0.12) ) 10%12
CH3OH (2.60 & 0.10) ) 10%12
GeH4 86 HCl (8.08 & 0.35) ) 10%13
Me2GeH2 364 425 800c(1043)d 1-C4H9Br (2.88 & 0.28) ) 10%12

a
krel = k(GeH2 + substrate)/k(GeXY + substrate): k(GeH2 + SO2 (3.35 & 0.12) ) 10%11
substrate) values taken from ref. 14 (GeH4, high pressure limit) and
C3H8 r3.1 ) 10%14
88 (Me2GeH2). b Based on data from ref. 34. c Based on data from
Me3SiH r6.2 ) 10%14
ref. 85. d Based on data from ref. 88. GeH4 r3.1 ) 10%14
Me2GeH2 r9.3 ) 10%14
C2H4 r1.0 ) 10%14
into the GeH bonds of the GeH4 and Me2GeH2. Me-for-H N2O r9.3 ) 10%14
substitution in germylenes is much more deactivating than in a
Ref. 36.
silylenes for insertion reactions. In the case of GeMe2 +
Me2GeH2, a reinvestigation85 (with a purer sample of
Me2GeH2) has indicated that no observable reaction occurs
(k o 9.3 ) 10%15 cm3 molecule%1 s%1), showing that in this Table 17 Comparison of addition rate constantsa of the dimethyl
heavy carbenes to unsaturates at 298 Kb
case GeMe2 is even less reactive than previously thought.88 A
low rate constant (7.5 ) 10%14 cm3 molecule%1 s%1) has also Substrate SiMe2 GeMe2 SnMe2
been found by Leighs group89 for the reaction of GeMe2 +
C2H4 2.2 ) 10 %11
2.0 ) 10 %11
o1.0 ) 10%14
Et3GeH in hexane solution. Ab initio calculations support the 1,3-C4H6 7.5 ) 10%11 1.2 ) 10%11 6.0 ) 10%11
idea that this is again a secondary barrier eect85. It is worth CH3CRCCH3 1.7 ) 10%10 3.4 ) 10%11 7.8 ) 10%12
noting finally, however, that in solution GeMe2 inserts rapidly a
Units: sm3 molecule1 s1. b
For original data sources see ref. 36.
with n-Bu3SnH (k = 2.3 ) 10%11 cm3 molecule%1 s%1)89
presumably via SnH insertion.
For the addition reactions of MeGeH34 and GeMe235 the
data again indicate deactivating eects of Me-for-H replace- the basis of end product analysis in hexane solution:90
ment in the germylene. The eects vary with pressure (reaction
SnMe2 Me3 SnH ! Me3 SnSnMe2 H 25
with C2H4) and the best estimates for reactions with alkenes in
general are factors of 4 to 5 per Me group.34 Thus for In view of the diculty of the GeMe2 + Me2GeH2 reaction,88
germylenes just as for silylenes, addition reactions are less reaction (25) is probably relatively slow.
sensitive to these substituent eects than insertion reactions. The addition reaction of SnMe2 with C2H4 also does not
For further comparisons interested readers are referred to the occur. In contrast relatively high rate constants were found for
original papers. reaction of SnMe2 with 1,3-butadiene and 2-butyne. These
particular results allow a comparison of the gas phase reactiv-
4.5.2 The kinetic behaviour of SnMe2 and comparisons with ity of the three dimethyl carbenes, SiMe2, GeMe2 and SnMe2,
SiMe2 and GeMe2. One of the driving motivations of this work the only such comparison currently possible. This is shown in
is to try to learn how, and understand why, reactivities change Table 17. For reaction of SnMe2 with C2H4 (and probably all
as one proceeds from silicon to germanium, thence to tin and simple alkenes), lack of reaction is almost certainly due to
finally to lead. Unfortunately beyond germanium there is very instability of the likely stannirane ring product. Ab initio
little kinetic information on heavy carbenes. The prototype calculations91 indicate little if any binding energy for this
stannylene, SnH2, has recently been identified by matrix molecule. For the reactions with butadiene and 2-butyne,
isolation spectroscopy and its ir spectrum reported.11c How- trends are a bit erratic but the indications are of fairly fast
ever no vibronic spectrum, useful for transient monitoring is reactions for all three species. Reaction with alkynes is still a
yet known although theoretical calculations of its ground state bit of a puzzle, since the likely stannirene product91 is also not
electronic structure have been made.11c Dimethylstannylene, strongly boundww.
SnMe2, on the other hand, has been created, detected and Reaction of SnMe2 with MeOH forms the donoracceptor
studied by time resolved means.10,36,90 It is (thus far) the least
adduct which has been seen in solution.90 Similar behaviour
reactive of the dimethyl heavy carbenes. There are as yet no has been found for GeMe2 + MeOH in solution92 and
such studies of PbMe2. In the gas phase, using SnMe4 photo- SiMe2 + MeOH in the gas phase.74
dissociation as the source of SnMe2,36 we obtained the rate The recent kinetic study of SnMe2 in hexane solution carried
constants (and rate constant limits) shown in Table 16. No out by Leighs group, in collaboration with ourselves and
measurable reaction of SnMe2 with C3H8, Me3SiH, GeH4 or others90 using the 1,1-dimethylstannacyclopent-3-ene photo-
Me2GeH2 was found to occur on the timescale of laser flash chemical precursor has clarified certain questions. In the
photolysis experiments. Eectively SnMe2 does not readily absence of reactive substrates the dimerisation reaction (26)
insert into CH, CC, SiH, SiC, GeH or GeC bonds.
There is, as yet, no kinetic study of insertion of SnMe2 into an ww Calculated binding enthalpies (kJ mol%1)91 for reactions of SnMe2
Sn-H bond although the reaction (25) is thought to occur on are: +1 with C2H4 and %35 with C2H2.

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is the main fate of SnMe2. While a few of the details of these calculations do not accord
with experiment, e.g. (a) SiMe2 + SiH4 has a calculated
2SnMe2 ! Me2 Sn SnMe2 26 activation energy of +26 kJ mol%1 rather than zero49 and
(b) SiMe2 has a lower calculated barrier for reaction with
GeH4 than with SiH4 at odds (apparently) with our findings in
This is similar to the behaviour of most silylenes and germy-
respect of reaction with Me2SiH2 and Me2GeH285 (see Table
lenes in solution, for example SiMe2,93 SiPh2,87 GeMe289 and
GePh2.94 For SnMe2, kinetic studies are complicated by the 13), nevertheless broad trends and general magnitudes are
fact that SnMe2 and Sn2Me4 have overlapping spectra. In the almost certainly correct and provide a useful reference in
gas phase studies so far carried out, it seems that insucient guiding future experimental studies.
concentration of SnMe2 has been generated for (26) to be
anything other that a minor side reaction, even in the presence 5. Conclusions and future prospects
of unreactive substrates.36,90 It has been shown, by RRKM
calculations, that reaction (26) should not be pressure depen- While there is still a lot to learn about the kinetics of reactions
dent under reaction conditions.90 It has been further demon- of silylenes and germylenes, the pattern of reactivity is broadly
established. Many reactions involve weakly bound complexes.
strated, by DFT calculations,90 that DH1(Me2SnQSnMe2) =
These appear to form easily and at the collision rate. Whether
+108 kJ mol%1 zz, which makes the double bond suciently
strong that reaction (26) should not be reversible at room the overall reaction occurs at the collision rate depends on
temperature unlike the analogues of (26) for more bulky secondary reaction barriers. GeH2 reactions seem to be
stannylenes. For discussion of the remaining reactions of slightly slower than SiH2 reactions. It is not wholly clear
SnMe2 listed in Table 16, the interested reader is referred to whether this is due to secondary barriers or innately lower
the original article.36 reactivity. There is a need for deeper understanding of the
At this point in time, any further comparisons of stanny- behaviour of these intermediate complexes. Low temperature
lenes based on absolute rate constants are not possible. The (sub ambient) kinetic studies, not yet undertaken, would throw
best overall perspective on likely trends in reactivity of the light on this.
dimethyl heavy carbenes is probably oered by the theoretical There remains much to be learned about pressure dependent
reactions, particularly for germylene and stannylene reactions.
calculations of Su.91 Su has calculated the potential energy
The exploration of high pressure limits for some of these
surfaces for the reactions of MMe2 (M = C, Si, Ge, Sn and
Pb) with CH4, SiH4, GeH4, C2H6, C2H4, C2H2 and CH3OH. reactions could benefit from other approaches such as the
The potential energy surfaces include details of the well depths use of vibrationally excited heavy carbenes (along the lines
of the pre-reaction complexes, the activation barriers and the employed by Buntine et al.95 in their study of CH2 1A1(0,1,0)).
enthalpy changes for product formation. The details are too Some of the most interesting kinetic eects are those of
many to be included in an article mainly devoted to kinetics, substituents. The widely diering magnitudes of merely repla-
but the main inferences we take from these calculations cing an H-atom by a methyl group (not to mention the even
(leaving out the behaviour of CMe2, dimethylcarbene itself) more dramatic of Cl-for-H substitution) show that these
are the following: eects are anything but straightforward. There is a lot more
(i) Barriers for reaction of all MMe2 with CH4 and C2H6 are to discover here.
too high to make experimental observation of these reactions The general notion that heavy carbenes will react more
readily with weakly bound than with strongly bound substrate
ever likely.
(ii) Barriers for reaction of MMe2 with SiH4 and GeH4 molecules has taken a knock with the finding that SiMe2 insert
increase as we descend Group 14. At the lower end (i.e. for faster into SiH than into GeH bonds. There may be further
SiMe2 and GeMe2), they are low enough to suggest reaction surprises in store.
might be fast enough to observe. It is clear that stannylenes (and we imagine plumbylenes) are
(iii) Barriers are non existent or very small for reaction of less reactive than silylenes and germylenes. Further investiga-
MMe2 with C2H4 and C2H2, provided the overall reaction is tion of these species should help to make clear whether this is a
exothermic. Only the PbMe2 reactions are endothermic. real kinetic eect or due to the thermodynamic instability of
(iv) Of all the classes of reaction studied, only the MMe2 + the likely products.
CH3OH reactions form strongly bound adducts, not diering Lastly there is still a need to find better photochemical
much in strength between MQSi and MQPb. All the adducts sources (and wavelengths) for the production of heavy car-
benes to minimise the formation of unwanted side products
have high barriers to rearrangement, increasing from Si to Pb.
This makes their (unimolecular) rearrangement unlikely to be (such as free radicals) and to avoid substrate photodecompo-
observable. sition.
(v) Overall exothermicities (%DH) decrease on descending
the Group for all classes of reaction. This means that reactions Acknowledgements
will tend to get increasingly more reversible on progressing
from Si to Pb. For SnMe2 and PbMe2 some reactions will not The authors would like to express their thanks to the many
occur for thermodynamic rather than kinetic reasons. colleagues and students who have participated in this work. In
particular we thank Najem Al-Rubaiey, Jim Baggott, Mark
zz Ref. 90 gives a useful table of dissociation values (H1, S1 and G1) Blitz, Ian Carpenter, Guy Dormer, Monty Frey, Nicola Gold-
for disilenes, digermenes and distannenes. berg, Lida Kefala, Phil Lightfoot and Ben Mason from the
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University of Reading; Sergey Boganov, Mikhail Egorov, 26 (a) J. W. Thoman, Jr and J. I. Steinfeld, Chem. Phys. Lett., 1986,
Valery Faustov, Irina Krylova and Oleg Nefedov from the 124, 35; (b) J. R. Fisher and F. W. Lampe, J. Photochem.
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Zelinsky Institute of Organic Chemistry (Moscow); Sarah 27 A. Campargue and R. Escribano, Chem. Phys. Lett., 1999, 315,
Bowes from Southampton University; Pat Cannady from 397.
Dow-Corning Corporation (USA) and Willie Leigh from 28 B. P. Mason, H. M. Frey and R. Walsh, J. Chem. Soc., Faraday
McMaster University (Canada). R. B. thanks the Spanish Trans., 1993, 89, 4405.
29 S. E. Boganov, M. P. Egorov, V. I. Faustov and O. M. Nefedov,
DGICYT for support under project BQU2002-03381 and in The Chemistry of Organic Germanium Tin and Lead Com-
the Ministerio de Educacion y Ciencia for support under pounds, ed. Z. Rappoport, Willey, Chichester, 2002, vol. 2, ch. 12,
project CTQ2006-10512/BQU. p. 749.
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Walsh, Chem. Phys. Lett., 1996, 260, 433.
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What Have We Learnt About Heavy Carbenes Through Laser Flash Photolysis Studies?

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INVITED ARTICLE www.rsc.org/pccp | Physical Chemistry Chemical Physics

Received 7th December 2006, Accepted 26th January 2007

Table 2 Some thermodynamic data for heavy methylenes

Species DHf1/kJ mol%1 DSSE/kJ mol%1 Ref.

Called the inert pair eect in ref. 15.

Fig. 1 Orbital diagram for the two lowest states of silylene.

particular complexes influence the kinetic course of many of

Table 1 Geometries of the heavy methylenes (1A1 states)

MH2 RMH/A Bond angle/1

2818 | Phys. Chem. Chem. Phys., 2007, 9, 28172835 This journal is !

Table 3 Energy release for some prototype heavy carbene reactions

Reaction DH1/kJ mol%1 Ref.

SiH2 + C2H4 - c-H2SiC2H4 %201 8,18

SiH2 + H2O - H3SiOH %305 21

highly resolved spectra means that a narrow line optical probe

It is true to say that while photodissociation of these pre-

3.2 Detection and monitoring

Table 4 Approximate absorption (monitoring) wavelengths for se-

Species Dl/nm lmax/nm Ref.

MeSiH 430520 ca. 493 31

3.4 Data processing

2820 | Phys. Chem. Chem. Phys., 2007, 9, 28172835 This journal is !

Under operating conditions, substrate concentrations are al-

a rate constant, kobs, linearly dependent on [substrate]. The

SiH2 + N2O 0.019 4.12 0.46

z The GeH2( ( (C2H2 intermediate, although a p-complex, is actually

2822 | Phys. Chem. Chem. Phys., 2007, 9, 28172835 This journal is !

Table 10 Calculated quantum chemical (ab initio) energy valuesa for

Complex Energy TS2(Energy) Level Ref.

Fig. 12 Schematic association potential energy surface for some

correlation between the calculated height of the secondary

Fig. 13 Typical set of pressure dependent rate constants of a heavy

2824 | Phys. Chem. Chem. Phys., 2007, 9, 28172835 This journal is !

and in these latter cases modelling can only be undertaken

z In these reactions, and most others in this section unless explicitly

alternative exit channel to form GeH2 + SiH4. It is therefore

Although the data were not fitted quantitatively, it was clear

2826 | Phys. Chem. Chem. Phys., 2007, 9, 28172835 This journal is !

% 9:3 & 2:8 kJ mol%1 =RT ln10

The Arrhenius parameters are very unusual for SiH2 reactions,

2828 | Phys. Chem. Chem. Phys., 2007, 9, 28172835 This journal is !

4.3 Reactions with complex kinetics

form to simple second order kinetics, albeit many of them with

The calculations show that direct insertion of SiH2 into the

Fig. 17 Rate constant pressure dependences for the reaction

Reaction T/K k/cm3 molecule%1 s%1 Ea/kJ mol%1 Ref.

SiH2 + SiMe4 296 o1.7 ) 10%13 416 78

SiH2 + N2 296 o3.0 ) 10%15 429 51

GeH2 + D2 293 o1.0 ) 10%14 411 52

barrier prohibits observation of this intermolecular reaction,

2830 | Phys. Chem. Chem. Phys., 2007, 9, 28172835 This journal is !

MeSiH3 2.0 1.05 215 1290 C2H4 3.2 1220 6.3d

Me2GeH2 364 425 800c(1043)d 1-C4H9Br (2.88 & 0.28) ) 10%12

2832 | Phys. Chem. Chem. Phys., 2007, 9, 28172835 This journal is !

2834 | Phys. Chem. Chem. Phys., 2007, 9, 28172835 This journal is !

6001. 81 R. Becerra and R. Walsh, Thermochemistry, in The Chemistry of

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