Inorganic Chemistry 5Th Edition Miessler Solutions Manual Full Chapter PDF

Inorganic Chemistry 5th Edition
Miessler Solutions Manual

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Chapter 9 Coordination Chemistry I: Structures and Isomers 123
CHAPTER 9: COORDINATION CHEMISTRY I: STRUCTURES AND

ISOMERS
9.1 Hexagonal: C2v C2v D2h
Hexagonal pyramidal: Cs Cs C2v
Trigonal prismatic: Cs C2v C2
Trigonal antiprismatic: Cs C2 C2h
The structures with C2 symmetry would be optically active.
9.2 a. dicyanotetrakis(methylisocyano)iron(II) or dicyanotetrakis(methylisocyano)iron(0)
b. rubidium tetrafluoroargentate(III) or rubidium tetrafluoroargentate(1–)
c. cis- and trans-carbonylchlorobis(triphenylphosphine)iridium(I) or cis- and trans-

carbon ylchlorobis(triphenylphospine)iridium(0)
d. pentaammineazidocobalt(III) sulfate or pentaammineazidocobalt(2+) sulfate
e. diamminesilver(I) tetrafluoroborate(III) or diamminesilver(1+) tetrafluoroborate(1–)

–
(The BF4 ion is commonly called “tetrafluoroborate.”)
9.3 a. tris(oxalato)vanadate(III) or tris(oxalato)vanadate(3–)
b. sodium tetrachloroaluminate(III) or sodium tetrachloroaluminate(1–)
c. carbonatobis(ethylenediamine)cobalt(III) chloride or
carbonatobis(ethy lenediamine)cobalt(1+) chloride
d. tris(2,2-bipyridine)nickel(II) nitrate or tris(2,2-bipyridine)nickel(2+) nitrate (The

IUPAC name of the bidentate ligand, 2,2-bipyridyl may also be used; this ligand is most
familiarly called “bipy.”)
e. hexacarbonylmolybdenum(0) (also commonly called “molybdenum hexacarbonyl”).

The (0) is often omitted.
9.4 a. tetraamminecopper(II) or tetraamminecopper(2+)
b. tetrachloroplatinate(II) or tetrachloroplatinate(2–)
c. tris(dimethyldithiocarbamato)iron(III) or tris(dimethyldithiocarbamato)iron(0)
d. hexacyanomanganate(II) or hexacyanomanganate(4–)
e. nonahydridorhenate(VII) or nonahydridorhenate(2–) (This ion is commonly called

“enneahydridorhenate.”)
Copyright © 2014 Pearson Education, Inc.

124 Chapter 9 Coordination Chemistry I: Structures and Isomers
9.5 a. triamminetrichloroplatinum(IV) or triamminetrichloroplatinum(1+)
b. diamminediaquadichlorocobalt(III) or diamminediaquadichlorocobalt(1+)
c. diamminediaquabromochlorocobalt(III) or diamminediaquabromochlorocobalt(1+)
d. triaquabromochloroiodochromium(III) or triaquabromochloroiodochromium(0)
e. dichlorobis(ethylenediamine)platinum(IV) or dichlorobis(ethylenediamine)platinum(2+)
or dichlorobis(1,2-ethanediamine)platinum(IV) or dichlorobis(1,2-
ethanediamine)platinum(2+)
f. diamminedichloro(o-phenanthroline)chromium(III) or diamminedichloro(o-
phenanthroline)chro mium(1+) or diamminedichloro(1,10-phenanthroline)chromium(III)
or diamminedichloro(1,10-phenanthroline)chromium(1+)
g. bis(2,2-bipyridine)bromochloroplatinum(IV) or bis(2,2-
bypyridine)bromochloroplatinum(2+)
or bis(2,2-bipyridyl)bromochloroplatinum(IV) or bis(2,2-
bipyridyl)bromochloroplatinum(2+)
h. dibromo[o-phenylene(dimethylarsine)(dimethylphosphine)]rhenium(II) or
dibrom o[o-phenylene(dimethylarsine)(dimethylphosphine)]rhenium(0) or
dibrom o[1,2-phenylene(dimethylarsine)(dimethylphosphine)]rhenium(II) or
dibrom o[1,2-phenylene(dimethylarsine)(dimethylphosphine)]rhenium(0)
i. dibromochlorodiethylenetriaminerhenium(III) or
dibrom ochlorodiethylenetriaminerhenium(0) or dibromochloro(2,2-
diam inodiethylamine)rhenium(III) or dibromochloro(2,2-
diam inodiethylamine)rhenium(0)
9.6 a. dicarbonylbis(dimethyldithiocarbamato)ruthenium(III) or
dicarbonylbis(dimethyldithiocarbamato)ruthenium(1+)
b. trisoxalatocobaltate(III) or trisoxalatocobaltate(3–)
c. tris(ethylenediamine)ruthenium(II) or tris(ethylenediamine)ruthenium(2+)
d. bis(2,2-bipyridine)dichloronickel(II) or bis(2,2-bipyridine)dichloronickel(2+)
9.7 a. Bis(en)Co(III)-µ-amido-µ-hydroxobis(en)Co(III)
4+
N N
H2
N N N
Co Co
N O N
H
N N

b. Diaquadiiododinitritopalladium(IV)
I H2O
ONO OH2 ONO I

Pd Pd
H2O ONO H 2O ONO
I I
I I
ONO OH2 ONO OH2

Pd Pd
ONO OH2 H 2O I
I ONO
I I
H 2O I I OH2
Pd Pd
ONO ONO ONO ONO
H2O OH2
enantiomers
c. Fe(dtc)3
S S
–
S CH3
S
S S S S
Fe Fe = C N
S S S S S
S H
S S
At low temperature, restricted rotation about the C—N bond can lead to additional
isomers as a consequence of the different substituents on the nitrogen. These isomers can
be observed by NMR.

9.8 a. triammineaquadichlorocobalt(III) chloride Isomers are of the cation:
+ + +
H2O Cl NH3
H3N Cl H3N OH2 H2O NH3

Co Co Co
H 3N NH3 H3N NH3 Cl NH3
Cl Cl Cl
cis trans
mer fac
b. -oxo-bis(pentammine-chromium(III)) ion
4+
H3N H3N H3N NH3
O
Cr Cr
H3N NH3
H3N NH3 NH3 NH3
c. potassium diaquabis(oxalato)manganate(III) Isomers are of the anion:
– – –
O O H2O
O O O O O O
Mn Mn Mn
H2O O O OH2 O O
H2O OH2 H2O
cis enantiomers trans

Cl NH3
9.9 a. cis-diamminebromochloroplatinum(II) Pt
Br NH3
b. diaquadiiododinitritopalladium(IV) H2O ONO

Pt
ONO OH2
O
O O C O
C C C CO
c. tri--carbonylbis(tricarbonyliron(0))
Fe Fe
OC CC CO
O O
9.10 O
CH2 C
H2 N O – = N O
O O N N
N N N N O N N O
M M M M
O O O O N O O N
N N O O
fac mer
9.11 M(AB)3
B B A A
A A A A B A A B
M M M M
B B B B A B B A
A A B B
fac mer
9.12 a. [Pt(NH3)3Cl3]+
+ Cl
+
NH 3
Cl NH3 H3N NH3

Pt Pt
Cl NH3 Cl NH3
Cl Cl
fac mer
b. [Co(NH3)2(H2O)2Cl2]+
+ + + +
NH3 Cl NH3 NH3
H 2O NH3 H 2O NH3 Cl OH2 Cl OH2

Co Co Co Co
Cl OH2 H 2O NH3 Cl OH2 H2 O Cl
Cl Cl NH3 NH3
+ +
OH2 H 2O
H 2O NH3 H 3N OH2
Co Co
Cl NH3 H3N Cl
Cl Cl
enantiomers

c. [Co(NH3)2(H2O)2BrCl]+
+ + + +
OH2 Cl NH3 NH3
H 3N Br H 2O NH3 Br OH2 Cl OH2

Co Co Co Co
H 3N Cl H 2O NH3 Cl OH2 H2 O Br
OH2 Br NH3 NH3
+ + + +
OH2 H2O OH2 H2O
H 2O NH3 H 3N OH2 H2 O NH3 H3 N OH2

Co Co Co Co
Br NH3 H 3N Br Cl NH3 H3N Cl
Cl Cl Br Br
enantiomers enantiomers
d. Cr(H2O)3BrClI
OH2 H2O
H2 O OH2 H2 O OH2
Cr Cr
Cl I I Cl
Br Br
enantiomers
OH2 OH2 OH2
Cl OH2 I OH2 Cl OH2

Cr Cr Cr
H2 O Br H 2O Br H2 O I
I Cl Br
e. [Pt(en)2Cl2]2+
2+ 2+ 2+
N N Cl
N N N N N N
Pt Pt Pt
Cl N N Cl N N
Cl Cl Cl
cis enantiomers trans

f. [Cr(o-phen)(NH3)2Cl2]+
+ +
+ +
N N
N N
N Cl N NH3
N NH3 H 3N N
Cr Cr
Cr Cr Cl NH3 H3N Cl
Cl NH3 H3N Cl
NH3 Cl
Cl Cl
enantiomers trans Cl ligands trans NH3 ligands
g. [Pt(bipy)2BrCl]2+ 2+ 2+
2+
Br N N
N N N Br Br N
Pt Pt Pt
N N Cl Cl
N N
Cl N N
enantiomers
h. Re(arphos)2Br2 Abbreviating the bidentate ligands As P :
Br Br P P
P P P As Br As As Br
Re Re Re Re
As As As P Br As As Br
Br Br P P
 
As As As As
Br P P Br Br P P Br
Re Re Re Re
Br P P Br Br As As Br
As As P P
   

i. Re(dien)Br2Cl
Cl Cl Br
N Br Br N N Cl
Re Re Re
N Br Br N N Br
N N N
Br Cl
N Cl N Br
Re Re
N N N N
Br Br
9.13 a. M(ABA)(CDC)
C A B B
A D C B C A A C
M M M M
B A D A D A A D
C C C C
b. M(ABA)(CDE)
C A A
A D C B B C
M M M
B A D A A D
E E E
B B
C A A C
M M
D A A D
E E
A A
C A A C
M M
D B B D
E E

9.14
A A A
C B A B B A
M M M
B C B C C B
A C C
A A C C
A B B A A A A A
M M M M
B C C B B B B B
C C C C
B B B B
A C C A A A A A
M M M M
B A B B B C C B
C C C C
9.15 a. The “softer” phosphorus atom bonds preferentially to the soft metal Pd (see Section 6.6.1).
b, c. Abbreviating the bidentate ligands N P :
Cl Cl P P
P P P N Cl N N Cl
Ni Ni Ni Ni
N N N P Cl N N Cl
Cl Cl P P
 
N N N N
Cl P P Cl Cl P P Cl
Ni Ni Ni Ni
Cl P P Cl Cl N N Cl
N N P P
   

9.16 a, b. Abbreviating the bidentate ligands N P and O S :
Cl Cl
S P S N
M M
O N O P
Cl Cl
N N P P
Cl P P Cl Cl N N Cl
M M M M
Cl O O Cl Cl O O Cl
S S S S
   
N N P P
Cl P P Cl Cl N N Cl
M M M M
Cl S S Cl Cl S S Cl
O O O O
   
N –
9.17 The single C–N stretching frequency indicates a trans

structure for the cyanides (the symmetric stretch of the C
C—N bonds is not IR active), while the two C–O bonds O
C
O
C
indicate a cis structure for the carbonyls (both the Co
symmetric and antisymmetric C–O stretches are IR Br Br
active). As a result, the bromo ligands are also cis. C

9.18 There are 18 isomers overall, six with the chelating ligand in a mer geometry and 12 with
the chelating ligand in a fac geometry. All are enantiomers. They are all shown below, with
dashed lines separating the enantiomers.
N N N N N N
P Br Br P P Br Br P P NH 3 H3N P
M M M M M M
As OH2 H2O As As NH3 H 3N As As OH2 H2 O As
NH3 NH3 OH2 OH2 Br Br
N N N N N N
P OH2 H2O P P NH3 H3 N P P OH2 H 2O P

M M M M M M
As Br Br As As Br Br As As NH3 H3N As
NH3 NH3 OH2 OH2 Br Br
NH3 NH3 OH2 OH2 NH3 NH3
P N N P P N N P P N N P
M M M M M M
As OH2 H2O As As NH3 H3N As As Br Br As
Br Br Br Br OH2 OH2
9.19 a.  b.  c.  d. 
9.20 All are chiral if the ring in b does not switch conformations.
9.21 20b  20c top ring: , bottom ring: 
O Mo S Mo
9.22 a, b. 1. Mo O Mo O
Mo S Mo O
O W O W
Cs C3v
O Mo S Mo
2. Mo O Mo S
Mo S Mo O
S W O W
Cs Cs
S Mo Mo S O Mo Mo O
Mo O O Mo Mo S S Mo
3.
Cr O O Cr Cr O O Cr
Se W W Se Se W W Se
C1 C1 C1 C1
Se Mo Mo Se O Mo Mo O
Mo O O Mo Mo Se Se Mo
Cr O O Cr Cr O O Cr
S W W S S W W S
C1 C1 C1 C1

S Mo S Mo
Mo Se Mo Se
Cr O W O
O W O Cr
Cs Cs
c. Yes, provided the structure has no symmetry or only Cn axes. Examples are the
structures with C1 symmetry in part a.
9.23 The 19F doublet is from the two axial fluorines (split by the equatorial fluorine). F
+
The 19F triplet is from the equatorial fluorine (split by the two axial fluorines). O
Os F
The two doubly bonded oxygens are equatorial, as expected from VSEPR O
considerations. Point group: C2v F
9.24 Examples include both cations and anions:
– – – – –
[Cu(CN)2] , [Cu2(CN)3] , [Cu3(CN)4] , [Cu4(CN)5] , [Cu5(CN)6]
[Cu2(CN)]+, [Cu3(CN)2]+, [Cu4(CN)3]+, [Cu5(CN)4]+, [Cu6(CN)5]+
Based primarily on calculations (rather than experimental data), Dance et al. proposed
linear structures such as the following:
–
[Cu(CN)2] : NC—Cu—CN
–
[Cu2(CN)3] : NC—Cu—CN—Cu—CN
–
[Cu3(CN)4] : NC—Cu—CN—Cu—CN—Cu—CN
+
[Cu2(CN)] : Cu—CN—Cu
+
[Cu3(CN)2] : Cu—CN—Cu—CN—Cu
+
[Cu4(CN)3] : Cu—CN—Cu—NC—Cu—CN—Cu
Where 2-coordinate copper appears in these ions, the geometry around the Cu is linear, as
expected from VSEPR.
9.25 The bulky mesityl groups cause sufficient crowding that the phosphine ligands can show
chirality (C3 symmetry) and can be considered as similar to left-handed (PL) and HC 3
right-handed (PR) propellers. If two P(mesityl)3 phosphines are attached in a CH3

linear arrangement to a gold atom, three isomers are possible:
H 3C
PL—Au—PL PR—Au—PR PL—Au—PR mesityl
(PR—Au—PL is equivalent to PL—Au—PR, as can best be seen with models.) NMR data
at low temperature support the presence of these isomers, which interconvert at higher
temperatures.

9.26 The point group is D3h. A representation  based on the nine 1s orbitals
of the hydride ligands is:
 

D3h E 2C3 3C2 h 2S3 3v 
 Re
 9 0 1 3 0 3

A1 1 1 1 1 1 0 z2 
E 2 –1 0 2 –1 0 (x, y), (x2–y2, xy) 
A2 1 1 –1 –1 –1 1 z 
E 2 –1 0 –2 1 0 (xz, yz) = H
The representation  reduces to 2 A1 + 2 E + A2 + ECollectively these representations

match all the functions for s (totally symmetric, matching A1), p, and d orbitals of Re, so all the s,
p, and d orbitals of the metal have suitable symmetry for interaction. (The strength of these
interactions will also depend on the match in energies between the rhenium orbitals and the 1s
orbital of hydrogen.)
9.27
NN NN
NN
O Cr O O Cr O
O Cr O
OO OO OO O
O OO OO
O Mn O O Mn
Mn O O Mn O O O
O O O O
O O OO O
O OO O OO O
O Cr O O Cr O
O Cr O
NN NN
NN
9.28 N
N N
O O
N Co N
N N
N O O N
N N
O O
O O
Co Co
O
O
O N O
N N
N N
N N N N
N N
N N
O N O
O O
Co Co
O O
O O
N N
N O O N
N N
N Co N
O O
N N

9.29 a. Cu(acacCN)2: D2h tpt: C2v

b. C6
9.30 All four metal-organic frameworks studied (MOF-177, Co(BDP), Cu-BTTri, Mg 2 (dobdc) ) are
significantly more effective at adsorbing carbon dioxide relative to adsorbing hydrogen. This is
attributed, in part, to the higher polarizability of CO 2 relative to that of H 2 . The formation of an
induced dipole in these gases by exposed cations within MOFs is an important prerequisite for
adsorption. The two MOF properties that most strongly correlate with CO 2 adsorption capacity
are MOF surface area and MOF accessible pore volume. As these values (tabulated below)
increase, the CO 2 adsorption capacity increases.
MOF Surface Area ( m2 g ) Accessible Pore Volume ( cm3 g )

MOF-177 4690 1.59
Co(BDP) 2030 0.93
Cu-BTTri 1750 0.713
Mg 2 (dobdc) 1800 0.573
The graphs in Figure 1 of the reference clearly indicate that Mg 2 (dobdc) adsorbs the most CO 2
at 5 bar. The arrangement and concentration of open Mg 2+ cation sites on the Mg 2 (dobdc)
surface is hypothesized to render this MOF more susceptible to CO 2 adsorption. This MOF,
along with Cu-BTTri, which also features exposed metal sites, are identified as the best prospects
for CO 2 H 2 separation.
9.31 The synthesis and application of amine-functionalized MOFs for CO 2 adsorption is the general
topic of the reference. While the M 2 (dobdc) series of MOFs were proposed as excellent
candidates for this functionalization (on the basis of their relatively large concentration of
exposed metal cation sites), their amine-functionalization proved difficult. This was attributed to
the relatively narrow MOF channels that may hinder amine diffusion into M 2 (dobdc) .
One hypothesized solution was to prepare a MOF with the M 2 (dobdc) structure-type, but with
larger pores. The wider linker dobpdc (below, along with dobdc for comparison) was used in the
hope of obtaining MOFs with larger pores.
O O
O O
O
O O
O
dobdc
O O
dobpdc

Amine-functionalized Mg 2 (dobpdc) was prepared by mixing H 4 (dobpdc) , magnesium bromide,

and a small solvent volume (a mixture of N,N’-diethylformamide and ethanol) in a Pyrex
container. The mixture was heated in a microwave reactor, and the M 2 (dobpdc) collected by
filtration after cooling. Dried samples of Mg 2 (dobpdc) were then heated for roughly one hour at
420 °C under dynamic vacuum. After this “activation” step, Mg 2 (dobpdc) was stirred with an
excess of N,N’-dimethylethylenediamine (mmen) in hexanes for one day. Subsequent heating
under vacuum resulted in removal of residual solvents to afford mmen-functionalized
Mg 2 (dobpdc) . The “activation” step was found necessary to completely remove residual N,N’-
diethylformamide from the Mg 2+ coordination sites.
9.32 This reference discusses application of porphyrin-containing MOFs where the porphyrin provides
a binding site for Fe(III) and Cu(II). The precursor to the porphyrin linker (TCPP) is provided
below; the resulting carboxylates of this linker permit its incorporation into the MOF.
HOOC COOH
N
H
N N
H
N
HOOC COOH
The metallation options include premetallation and postmetallation. In premetallation,

H 4 -TCPP-Cu and H 4 -TCPP-FeCl , respectively, are used as reactants for the MOF synthesis. In
this case, the porphyrin linker and its bound metal ion are installed simultaneously into the MOF.
This general approach afforded MOF-525-Cu, MOF-545-Fe, and MOF-545-Cu. MOF-525-Fe
could not be obtained via this strategy. For this MOF, postmetallation was employed, via the
reaction of MOF-525 with Fe(III) chloride; Fe(III) ions were introduced into the MOF-525
porphyrin linkers via this method.
In terms of similarities and differences, MOF-545 can be metallated with both Fe(III) and Cu(II)
via a premetallation strategy, while MOF-525 requires alternate procedures for incorporation of
Cu(II) (premetallation) and Fe(III) (postmetallation), respectively.

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agriculture their sole resource, 138.
Volney describes the American habits of diet, i. 44.
Voltaire, i. 161.
Wagner, Jacob, i. 236.

Ware, Henry, i. 311.
Warren, Dr. J. C., his description of Boston customs in 1800, i.
91.
Washington city in 1800, i. 30.
Washington, President, opinion of American farming-lands, i. 35;
his support of a national bank, 65;
on emancipation in Pennsylvania and its effects, 135;
establishes the precedent of addressing Congress in a
speech, 247;
his personal authority, 262, 320.
Water communication in 1800, i. 8.
Waterhouse, Dr., i. 93.
Webster, Noah, i. 62, 105.
Weld, Rev. Abijah, of Attleborough, i. 21.
Weld, Isaac, Jr., an English traveller, describes condition of inns
in America, i. 46, 52;
describes Princeton, 129;
quoted, 136;
at Wilmington, 182.
West, Benjamin, i. 127.
West Indian trade, English policy toward, ii. 318;
value of, to England, 331, 413, 415.
West Point Military Academy established, i. 301.
Whitney, Eli, i. 181.
Whittemore, Asa, i. 182.
Whitworth, Lord, British minister at Paris, Napoleon’s
announcement to, ii. 19.
Wilkinson, James, Brigadier-General and governor of the
Louisiana Territory, ii. 220;
portrayed by Turreau, 406;
his relations with Burr, 408.
William and Mary, college of, i. 136.
Wilson, Alexander, describes New England in 1808, i. 19;
on North Carolina, 36, 57, 124.
Wilson, Judge, i. 127.
Wistar, Dr. Caspar, i. 127.
Wordsworth, i. 94;
his lines on America, 169, 172.
Wythe, George, i. 133.
X. Y. Z. affair, i. 355, 358, 359.
Yale College, i. 106.

Yazoo Act, i. 304.
Yazoo Compromise, ii. 210;
Madison’s measure, 211;
vote upon, 217.
(See Georgia.)
Yrujo, Don Carlos Martinez, Spanish minister, his intimate
relations with Jefferson, i. 425;
writes to Morales with respect to the right of deposit, 427;
announces the restoration of the right of deposit, ii. 3;
protests against the sale of Louisiana, 92, 252 et seq.;
his anger, 258, 389;
obtains from American lawyers an opinion, 259;
attacks Madison, 260;
his affair with Jackson, 265;
visits Jefferson at Monticello, 266;
publishes his counter statement as to his affair with Jackson,
268;
relations of, with White House, 362;
indiscretion, 368;
at the White House, 369;
concerts reprisals with Merry, 373.
END OF VOL. II.
FOOTNOTES:
[1] Cabinet Memoranda of Mr. Jefferson, April 8, 1803;
Jefferson MSS.
[2] Madison to Livingston and Monroe, April 18 and 20, 1803;
State Papers, ii. 555.
[3] Livingston to Madison, Nov. 11, 1802; State Papers, ii. 526.
[4] State Papers, ii. 556.
[5] Yrujo to Madison, Notes of April 19 and 20, 1803; MSS.
State Department Archives.
[6] Bonaparte to Decrès, 6 Fructidor, An x. (Aug. 24, 1802);
Correspondance, viii. 4.
[7] Instructions secrètes pour le Capitaine-Général de la
Louisiane, approuvées par le Premier Consul le 5 Frimaire, An xi.
(Nov. 26, 1802); Archives de la Marine, MSS.
[8] Livingston to Madison, Feb. 18, 1803; State Papers, ii. 533.
[9] Talleyrand to Bernadotte, 24 Nivôse, An xi. (Jan. 14, 1803);
Archives des Aff. Étr., MSS.
[10] Correspondance, viii. 145; Bonaparte to Decrès, 28
Frimaire, An xi. (Dec. 19, 1802).
[11] Correspondance, viii. 146; Bonaparte to Victor, 25
Frimaire, An xi. (Dec. 16, 1802).
[12] Livingston to Madison, Dec. 20, 1802; State Papers, ii.
528.
[13] Rochambeau to Decrès, 16 Frimaire, An xi. (Dec. 7,
1802); Archives de la Marine, MSS.
[14] Correspondance, viii. 201; Bonaparte to Decrès, 16
Pluviôse, An xi. (Feb. 5, 1803).
[15] Lucien Bonaparte et ses Mémoires, Th. Jung, ii. 165, n.;
Lanfrey’s Napoleon, ii. 495.
[16] Livingston to Madison, Feb. 18, 1803; State Papers, ii.
533.
[17] Beurnonville to Talleyrand, 15 Ventôse, An xi. (March 6,
1803); Archives des Aff. Étr., MSS.
[18] Cevallos to Beurnonville, March 10, 1803; Archives des
Aff. Étr., MSS.
[19] Livingston to Madison, March 12, 1803; State Papers, ii.
547.
[20] Amiot to Decrès, 19 Germinal, An xi. (April 9, 1803);
Archives de la Marine, MSS.
[21] Claims Convention, Aug. 11, 1802; State Papers, ii. 476.
[22] Madison to Pinckney, May 11, 1802; State Papers, ii. 517.
[23] Cevallos to Pinckney, May 4, 1803; State Papers, ii. 557.
[24] Rufus King to Madison, April 2, 1803; State Papers, ii.
551.
[25] History of Louisiana, Barbé Marbois, p. 277.
[26] History of Louisiana, Barbé Marbois, p. 263.
[27] Marbois’s Louisiana, p. 274.
[28] Livingston to Madison, April 11, 1803; State Papers, ii.
552.
[29] Livingston to Talleyrand, Jan. 10, 1803; Livingston to
Bonaparte, Feb. 27, 1803; State Papers, ii. 531, 539.
[30] Memoir of James Monroe, 1828; Colonel Mercer’s
Journal, p. 55.
552.
552, 544.
554.
[34] Lucien Bonaparte et ses Mémoires, Th. Jung, ii. 121–192.
[35] Correspondence, viii. 289.
[36] Monroe’s Memoranda, Monroe MSS., State Department
Archives.
[37] Livingston to Madison, May 3, 1804; MSS. State
Department Archives.
Archives.
[39] Draft of Convention in Monroe’s writing, Monroe MSS.,
State Department Archives.
[40] State Papers, ii. 507–509.
[41] Marbois, Louisiana, pp. 283, 286.
552.
[43] Monroe to Madison, April 19, 1803; State Department
Archives.
[44] Madison to Livingston and Monroe, March 2, 1803; State
Papers, ii. 540.
[45] Livingston to Madison, May 3, 1804; View of the Claims,
etc., by a Citizen of Baltimore, p. 75.
[46] View of the Claims, etc., by a Citizen of Baltimore. 1829.
[47] Livingston to Madison, Nov. 15, 1803; State Papers, ii.
573. Diary of John Quincy Adams, v. 433. Memoir of James
Monroe, 1828.
[48] Marbois’s Louisiana, pp. 311, 312.
[49] Marbois’s Louisiana, p. 276.
[50] Talleyrand to Decrès, 4 Prairial, An xi. (May 24, 1803);
[51] D’Azara to Talleyrand, June 6, 1803; Archives des Aff.
Étr., MSS.
[52] Beurnonville to Talleyrand, 24 Prairial, An xi. (June 13,
[53] Talleyrand to Beurnonville, 3 Messidor, An xi. (June 22,
[54] Madison to Livingston and Monroe, March 2, 1803; State
Papers, ii. 543.
[55] Jefferson to Monroe, Jan. 13, 1803; Works, iv. 455.
552.
[57] Ibid., July 30, 1802; State Papers, ii. 519.
[58] Ibid., May 12, 1803; State Papers, ii. 557.
[59] Ibid., May 20, 1803; State Papers, ii. 561.
[60] Livingston and Monroe to Madison, June 7, 1803; State
Papers, ii. 563–565.
[61] Livingston to Madison, May 20, 1803; Nov. 15, 1803;
State Papers, ii. 561, 573.
[62] Jefferson to Thomas Cooper, Nov. 29, 1802; Works, iv.
452.
[63] Report of the Secretary of the Treasury, Dec. 16, 1802.
Annals of Congress, 1802–1803, 1276.
[64] Lincoln to Jefferson, Jan. 10, 1803; Jefferson MSS.
[65] Gallatin to Jefferson, Jan. 13, 1803; Gallatin’s Works, i.
112.
[66] Jefferson to Governor McKean, Feb. 19, 1803; Jefferson
MSS.
[67] Jefferson to Colonel Hawkins, Feb. 18, 1803; Works, iv.
565.
[68] Jefferson to Levi Lincoln, June 8, 1803; Jefferson MSS.
[69] Amendment to the Constitution; Jefferson MSS.
[70] Gallatin to Jefferson, July 9, 1803; Works, i. 127.
[71] Robert Smith to Jefferson, July 9, 1803; Jefferson MSS.
[72] Jefferson to Breckenridge, Aug. 12, 1803; Works, iv. 498.
[73] Jefferson to Paine, Aug. 18, 1803; Jefferson MSS.
[74] Jefferson to Madison, Aug. 18, 1803; to R. Smith, Aug.
23; Jefferson MSS.
[75] Jefferson to Madison, Aug. 25; to Lincoln, Aug. 30, 1803;
Works, iv. 501–505; to Gallatin, Aug. 23, 1803; Gallatin’s Works, i.
144.
[76] W. C. Nicholas to Jefferson, Sept. 3, 1803; Jefferson
MSS.
[77] Jefferson to W. C. Nicholas, Sept. 7, 1803; Works, iv. 505.
[78] Yrujo to Madison, Sept. 4, Sept. 27, Oct. 12, 1803; State
Papers, ii. 569, 570.
[79] Morris to H. W. Livingston, Nov. 25, 1803. Writings of
Gouverneur Morris, iii. 185.
[80] Documents relating to New England Federalism, pp. 156,
157; Diary of J. Q. Adams, i. 267.
[81] Examination of the Decision of the Supreme Court in the
case of Dred Scott. By Thomas H. Benton, p. 55.
[82] Annals of Congress, 1803–1804, p. 514.
[83] Act of October 31, 1803. Annals of Congress, 1803–1804.
App. p. 1245.
[84] Diary of J. Q. Adams (Jan. 10, 1804), i. 287.
[85] American Insurance Company and Others v. Canter
(January Term, 1828), 1 Peters’s Reports, 511–546.
[86] Jefferson to Gallatin, Dec. 13, 1803; Works, iv. 518.
[87] Pichon to Talleyrand, 16 Fructidor, An xii. (Sept. 3, 1804);
[88] Dec. 8, 1803; Annals of Congress, 1803–1804, p. 751.
[89] Remarks on the Message, Gallatin’s Writings, i. 156;
Gallatin to Jefferson, Oct. 6, 1803; ibid., i. 162.
[90] Jefferson to R. Smith, Oct. 10, 1803; Jefferson MSS.
[91] Speech of John Randolph, March 22, 1804; Annals of
Congress, 1803–1804, p. 1221.
[92] Message of Feb. 3, 1803; Annals of Congress, 1802–
1803, p. 460.
[93] Jefferson to General Knox, March 27, 1801; Works, iv.
386.
[94] Cranch’s Reports, i. 153.
[95] Annals of Congress, 1804–1805, pp. 673–676.
[96] Jefferson to Nicholson, May 13, 1803; Works, iv. 486.
[97] Macon to Nicholson, Aug. 6, 1803; Nicholson MSS.
[98] Jan. 5, 1804; Annals of Congress, 1803–1804, p. 805.
[99] Diary of J. Q. Adams, i. 299.
[100] Ibid., i. 301–302. Pickering to George Cabot, Jan. 29,
1804; Pickering to Theodore Lyman, Feb. 11, 1804; New England
Federalism, pp. 340, 344.
[101] New England Federalism, pp. 106, 146, 342, 352;
Plumer’s Life of Plumer, pp. 284–311.
[102] Pickering to George Cabot, Jan. 29, 1804; Lodge’s
Cabot, p. 337.
[103] Roger Griswold to Oliver Wolcott, March 11, 1804;
Hamilton’s History of the Republic, vii. 781; New England
Federalism, p. 354.
[104] Cabot to Pickering, March 7, 1804; New England
Federalism, p. 353.
[105] Cabot to Pickering, Feb. 14, 1804; Lodge’s Cabot, p.
341.
[106] Tapping Reeve to Uriah Tracy, Feb. 7, 1804; Lodge’s
Cabot, p. 442.
[107] Theodore Lyman to Pickering, Feb. 29, 1804; Lodge’s
Cabot, p. 446.
[108] An Examination of the various Charges against Aaron
Burr, by Aristides. December, 1803.
[109] De Witt Clinton to Jefferson, Nov. 26, 1803; Jefferson
MSS.
[110] Jefferson to De Witt Clinton, Dec. 2, 1803; Jefferson
MSS.
[111] Jefferson to Governor Clinton, Dec. 31, 1803; Works, iv.
520.
[112] The Anas, Jan. 26, 1804; Works, ix. 204.
[113] Hamilton’s Works, vii. 851.
[114] Pickering to Rufus King, March 4, 1804; Lodge’s Cabot,
p. 447.
[115] Rufus King to Pickering, March 9, 1804; Lodge’s Cabot,
p. 450.
[116] Roger Griswold to Oliver Wolcott, March 11, 1804;
Hamilton’s History, vii. 781; New England Federalism, p. 354.
[117] George Cabot to Rufus King, March 17, 1804; Lodge’s
Cabot, p. 345.
[118] Hamilton’s History, vii. 787.
[119] New England Federalism, p. 148.
[120] Life of Plumer, p. 299.
[121] Hamilton’s History, vii. 806.
[122] Hamilton’s History, vii. pp. 816–819.
[123] Hamilton to Sedgwick, July 10, 1804; Works, vi. 567.
[124] Jefferson to Granger, March 9, 1814; Works, vi. 329.
[125] Jefferson to Granger, April 16, 1804; Works, iv. 542.
[126] Gallatin to Badollet, Oct. 25, 1805; Adams’s Gallatin, p.
331.
[127] Dallas to Gallatin, Oct. 16, 1804; Adams’s Gallatin, p.
326.
[128] Jefferson to Dr. Logan, May 11, 1805; Works, iv. 575.
[129] A. J. Dallas to Gallatin, Jan. 16, 1805; Adams’s Gallatin,
p. 327.
[130] Jefferson to Dr. Logan, May 11, 1805; Works, iv. 575.
[131] Dallas to Gallatin, April 4, 1805; April 21, 1811; Adams’s
Gallatin, pp. 333, 439.
[132] Jefferson to Volney, Feb. 8, 1805; Works, iv. 573.
[133] Jefferson to J. F. Mercer, Oct. 9, 1804; Works, iv. 563.
[135] See vol. i. p. 305.
[136] Diary of J. Q. Adams (Feb. 1, 1805), i. 343.
[137] Jefferson to General Smith, May 4, 1806; Works, v. 13.
[139] Diary of J. Q. Adams (Nov. 29, 30, 1804), i. 318.
[140] Boston Centinel, Jan. 9, 1805.
[141] Diary of J. Q. Adams (Dec. 21, 1804), i. 322.
[142] Ibid. (Dec. 24, 1804), i. 324, 325.
[144] Ibid., i. 361, 362.
[145] Diary of J. Q. Adams (March 1, 1805), i. 364.
[146] Randolph to Nicholson, April 30, 1805; Adams’s
Randolph, p. 157.
[147] Diary of J. Q. Adams (March 2, 1805), i. 367.
[148] Jefferson to Thomas Ritchie, Dec. 25, 1820; Works, vii.
192.
[149] Livingston to Madison, Nov. 15, 1803; State Papers, ii.
573, 574.
[150] Jefferson to Breckenridge, Aug. 12, 1803; Works, iv.
498.
[151] Madison to Pinckney, July 29, 1803; State Papers, ii.
614.
[152] Madison to Monroe, July 29, 1803; State Papers, ii. 626.
[153] Jefferson to Madison, Aug. 25, 1803; Works, iv. 501.
[154] Pinckney to Madison, Aug. 15, 1802; State Papers, ii.
482.
[156] Yrujo to Madison, Sept. 4 and 27, 1803; State Papers, ii.
569.
[157] Yrujo to Cevallos, Aug. 3, 1803; MSS. Spanish Archives.
[158] Yrujo to Cevallos, Sept. 12, 1803; MSS. Spanish
Archives.
[159] Yrujo to Cevallos, Nov. 5, 1803; MSS. Spanish Archives.
[160] Jefferson to Dupont, Nov. 1, 1803; Works, iv. 508.
[163] Jefferson to William Dunbar, March 13, 1804; Works, iv.
537.
[164] Madison to Livingston, Jan. 31, 1804; State Papers, ii.
574.
[165] Madison to Livingston, March 31, 1804; State Papers, ii.
575.
[166] Journal of Executive Sessions, Jan. 9, 1804.
[167] Madison to Pinckney, Jan. 31, 1804; State Papers, ii.
614.
[168] Madison to Pinckney, Feb. 6, 1804; State Papers, ii. 615.
[169] Yrujo to Madison, March 7, 1804; MSS. State
[170] Gallatin to Jefferson, October, 1804; Gallatin’s Works, i.
211.
575.
[172] Proclamation of May 30, 1804; State Papers, ii. 583.
[173] Message of Nov. 8, 1804. Annals of Congress, 1804–
1805, p. 11.
[174] Pichon to Talleyrand, 18 Brumaire, An xiii. (Nov. 9,
[175] Madison to Jefferson, Oct. 2, 1804; Jefferson MSS.
[176] Note du Premier Consul, 2 Floréal, An xi. (April 22,
1803); Correspondance, viii. 288.
[177] Turreau to Talleyrand, 23 Floréal, An xiii. (May 13, 1805);
[178] Turreau to Talleyrand, 6 Pluviôse, An xii. (Jan. 27, 1805);
Madison to Pinckney, July 29, 1803; State Papers, ii. 614.
[180] Madison to Pinckney, Oct. 12, 1803; State Papers, ii.
570.
[181] Madison to Jefferson, April 9, 1804; Jefferson MSS.
[182] Pinckney to Madison, Aug. 2, 1803; State Papers, ii.
597.
[183] Cevallos to Pinckney, Aug. 23, 1803; State Papers, ii.
604.
[184] Beurnonville to Talleyrand, 18 Nivôse, An xii. (Jan. 9,
[185] Talleyrand to D’Hervas, 12 Nivôse, An xii. (Jan. 3, 1804);
[186] Beurnonville to Talleyrand, 21 Nivôse, An xii. (Jan. 12,
[187] Cevallos to Pinckney, Feb. 10, 1804; State Papers, ii.
583.
[188] Yrujo to Madison, May 15, 1804; State Papers, ii. 583.
[189] Pinckney to Cevallos, June 1, 1804; State Papers, ii.
618.
[190] Beurnonville to Talleyrand, 18 Prairial, An xii. (June 7,
[191] Cevallos to Pinckney, July 2, 1804; State Papers, ii. 619.
[192] Pinckney to Cevallos, July 5, 1804; State Papers, ii. 620.
[193] Cevallos to Pinckney, July 8, 1804; State Papers, ii. 620.
[194] Pinckney to Cevallos, July 14, 1804; State Papers, ii.
621.
[195] Pinckney to Madison, July 20, 1804; MSS. State
[196] Pinckney to Madison, July 20, 1804; MSS. State
[197] Vandeul to Talleyrand, 7 Thermidor, An xii. (July 26,
[198] Vandeul to Talleyrand, 18 Thermidor, An xii. (Aug. 6,
[199] Yrujo to Madison, Oct. 13, 1804; State Papers, ii. 624.
[200] Madison to Yrujo, Oct. 15, 1804; State Papers, ii. 625.
[201] Madison to Monroe, Oct. 26, 1804; State Papers, ii. 631.
[202] Madison to Monroe, Nov. 9, 1804; Works, ii. 208.
[203] Madison to Monroe, Nov. 9, 1804; Works, ii. 208.
[204] Monroe to Madison, July 20, 1803; MSS. State
Archives.
[206] Skipwith to Madison, Feb. 21, 1804; State Department
Archives.
[207] Gouverneur Morris to Livingston, Nov. 28, 1803;
Sparks’s Morris, iii. 188.
[208] Vandeul to Talleyrand, July 26 and Aug. 6, 1804;
[209] Gravina to Talleyrand, July 24, 1804; Archives des Aff.
Étr., MSS. Cevallos to Monroe and Pinckney, 16 Feb. 1805; State
Papers, ii. 643.
[210] Talleyrand to Turreau (No. 99), 20 Thermidor, An xii.
(Aug. 8, 1804); Archives des Aff. Étr., MSS.
[211] Talleyrand to Turreau (No. 101), 27 Thermidor, An xii.
(Aug. 15, 1804); Archives des Aff. Étr., MSS.
[212] Instructions secrètes pour le Capitaine-Général de la
Louisiane, approuvées par le Premier Consul le 5 Frimaire, An xi.
(Nov. 26, 1802), Archives de la Marine, MSS.
575.
[214] Cf. Memoir upon the Negotiations between Spain and
the United States of America. By Don Luis de Onis, Madrid, 1820,
Washington, 1821; pp. 146, 147.
[215] Talleyrand to Gravina, 12 Fructidor, An xii. (Aug. 30,
[216] Jefferson to Madison, July 5, 1804; Works, iv. 550.
[217] Madison to Monroe, April 15, 1804; State Papers, ii. 627.
Madison to Monroe and Pinckney, July 8, 1804; State Papers, ii.
630.
[218] Monroe to Talleyrand, Nov. 8, 1804; State Papers, ii.
634.
[219] Monroe to Madison, Dec. 16, 1804; MSS. State
[220] Armstrong to Madison, Dec. 24, 1804; MSS. State
[221] Diary at Aranjuez, April 22, 1805; MSS. State
[222] Monroe to Madison, Dec. 16, 1804; MSS. State
[223] Armstrong to Madison, Dec. 24, 1804; MSS. State
[224] Rapport à l’Empereur, 28 Brumaire, An xii. (Nov. 19,
[225] Talleyrand to Armstrong, Dec. 21, 1804; State Papers, ii.
635.
[226] 28 George III. c. 6.
[227] Additional Instructions of Nov. 6, 1793; State Papers, i.
430.
[228] Reeves’s Law of Shipping and Navigation, part ii. chap.
iii.
[229] Appendix to 4 Robinson, 6.
[230] Advocate-General’s Report, March 16, 1801; State
Papers, ii. 491.
[231] See vol. i. p. 214.
[232] Thoughts on Commerce and Colonies, by Charles
Bosanquet.
[233] Thornton to Grenville, March 7, 1801; MSS. British
Archives.
[234] Act of Jan. 21, 1801, Statutes at Large of Virginia, New
Series, ii. 302.
[235] Thornton to Grenville, June 1, 1802; MSS. British
Archives.
[236] Trial of Isaac Williams, Hartford, 1799; Wharton’s State
Trials, 653. Shanks v. Dupont, 3 Peters, 242.
[237] 6 Anne, c. 20.
[238] Rufus King to Madison, April 12, 1801; State Papers, ii.
490.
[239] Liston to Grenville (private), May 7, 1800; MSS British
Archives.
[240] Thornton to Grenville, March 7, 1801; MSS. British
Archives.
[241] Thornton to Hawkesbury, Oct. 25 and Nov. 26, 1802:
MSS. British Archives.
[242] Thornton to Hawkesbury, July 3, 1802; MSS. British
Archives.
[243] Thornton to Hawkesbury, Dec. 31, 1802; MSS. British
Archives.
[244] Thornton to Hawkesbury, Jan. 3, 1803; MSS. British
Archives.
[245] Thornton to Hawkesbury, Jan. 31, 1803; MSS. British
Archives.
[246] See p. 2.
[247] Thornton to Hawkesbury, May 30, 1803; MSS. British
Archives.
[248] Pichon to Talleyrand, 8 Pluviôse, An xi. (Jan. 28, 1803);
[249] Pichon to Talleyrand, 14 Prairial, An xii. (June 3, 1803);
[250] Pichon to Talleyrand, 18 Messidor, An xii. (July 7, 1803);
[251] Jefferson to Mazzei, July 18, 1804; Works, iv. 552.
[252] Pichon to Talleyrand, 1 Ventôse, An xi. (Feb. 20, 1803);
[253] Pichon to Talleyrand, 18 Messidor, An xii. (July 7, 1803);
[254] Jefferson to Earl of Buchan, July 10, 1803; Works, iv.
493.
[255] Jefferson to General Gates, July 11, 1803; Works, iv.
494.
[258] Gallatin to Jefferson, Aug. 18, 1803; Gallatin’s Works, i.
140.
[259] King to Madison, April 10, 1802; MSS. State Department
Archives.
[260] Merry to Hammond, Dec. 7, 1803; MSS. British
Archives.
[261] Thornton to Hawkesbury, Dec. 9, 1801; MSS. British
Archives.
[262] Life of William Plumer, p. 245.
[263] Jefferson’s Works, ix. 454.
[264] Life of William Plumer, p. 242.
[265] Life of Joseph Story, pp. 151, 158.
[266] Pichon to Talleyrand, 15 Pluviôse, An xii. (Feb. 5, 1804);
[267] Merry to Hawkesbury, Dec. 6, 1803; MSS. British
Archives.
[268] Yrujo to Cevallos, Feb. 7, 1804; MSS. Spanish Archives.
[269] Merry to Hammond, Dec. 7, 1803; MSS. British
Archives.
[270] Madison to Monroe, 19 Jan., 1804. Madison MSS., State
Department Archives. Merry to Hawkesbury, 30 Jan., 1801. MSS.
British Archives.
[271] Pichon to Talleyrand, 15 Pluviôse, An xii. (Feb. 5, 1804);
Archives.
[273] Pichon to Talleyrand, 27 Pluviôse, An xii. (Feb. 13,
[274] Jefferson to Monroe, Jan. 8, 1804; Monroe MSS., State
Department Archives. Cf. Madison to Monroe, 16 Feb. 1804.
Madison’s Works, ii. 195–199.
[275] Pichon to Talleyrand, 30 Pluviôse, An xii. (Feb. 16,
[277] Ibid.
Archives.
Archives.
[280] Diary of J. Q. Adams (Oct. 31, 1803), i. 269.
Archives.
Archives.
[283] Merry to Hawkesbury, Jan. 20, 1804; Jan. 30, 1804;
MSS. British Archives.
[284] Thornton to Hammond, Jan. 29, 1804; MSS. British
Archives.
[285] Merry to Hawkesbury, Jan. 30, 1804; MSS. British
Archives.
[286] Merry to Hawkesbury, March 1, 1804; MSS. British
Archives.
[287] Merry to Harrowby, July 18, 1804; MSS. British Archives.
[288] Madison to Jefferson, Aug. 28, 1804; Jefferson MSS.
[289] Merry to Hawkesbury, June 2, 1804; MSS. British
Archives.
[290] Merry to Harrowby, Aug. 6, 1804; MSS. British Archives.
[291] Merry to Harrowby, March 4, 1805; MSS. British
Archives.
[292] Merry to Harrowby, March 29, 1805; MSS. British
Archives.
[293] Remonstrance of the People of Louisiana, Dec. 31,
1804; Annals of Congress, 1804–1805, Appendix, p. 1597.
[294] Report of Committee, Jan. 25, 1805; Annals of
Congress, 1804–1805, p. 1014.
[296] Merry to Harrowby, (No. 14), March 29, 1805; MSS.
British Archives.
[297] Merry to Harrowby, (No. 15), most secret, March 29,
1805.
[298] Pichon to Talleyrand, 16 Fructidor, An xii. (Sept. 3,
[300] Diary of J. Q. Adams (Nov. 23, 1804), i. 316.
[301] Turreau to Talleyrand, 27 Janvier, 1805; Archives des
Aff. Étr., MSS.
[302] Turreau to Talleyrand, 9 Mars, 1805; Archives des Aff.
Étr., MSS.
[303] Affidavit of Peter Derbigny, Aug. 27, 1807. Clark’s Proofs
against Wilkinson; Note 18. App. p. 38.
[304] Adams’s Randolph, p. 157.
[305] Strictures, etc., on the Navigation and Colonial System
of Great Britain. London, 1804.
[306] Claims of the British West Indian Colonists. By G. W.
Jordan. London, 1804.
[307] Lowe’s Enquiry, 4th edition, 1808.
[308] Anti-Jacobin Review, August, 1807, p. 368; Introduction
to Reports, etc., on Navigation, p. 22; Atcheson’s American
Encroachments, London, 1808, p. lxxvii; Baring’s Inquiry, London,
1808, p. 73.
[309] Monroe to Madison, June 3, 1804; State Papers, iii. 92.
[310] Monroe to Madison, Aug. 7, 1804; State Papers, iii. 94.
[311] Monroe to Madison, June 3, 1804; State Papers, iii. 92.
[312] Monroe to Madison, Sept. 8, 1804; MSS. State
[313] Harrowby to Merry, Nov. 7, 1804; MSS. British Archives.
[314] Life of General William Eaton, Brookfield, 1813, p. 262.
[315] Life of Eaton, p. 328.
Transcriber’s Notes:
1. Obvious printers’, punctuation and spelling errors have been corrected

silently.
2. Where hyphenation is in doubt, it has been retained as in the original.
3. Some hyphenated and non-hyphenated versions of the same words have

been retained as in the original.
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CHAPTER 9: COORDINATION CHEMISTRY I: STRUCTURES AND

9.2 a. dicyanotetrakis(methylisocyano)iron(II) or dicyanotetrakis(methylisocyano)iron(0)

b. rubidium tetrafluoroargentate(III) or rubidium tetrafluoroargentate(1–)

c. cis- and trans-carbonylchlorobis(triphenylphosphine)iridium(I) or cis- and trans-

d. pentaammineazidocobalt(III) sulfate or pentaammineazidocobalt(2+) sulfate

e. diamminesilver(I) tetrafluoroborate(III) or diamminesilver(1+) tetrafluoroborate(1–)

9.3 a. tris(oxalato)vanadate(III) or tris(oxalato)vanadate(3–)

b. sodium tetrachloroaluminate(III) or sodium tetrachloroaluminate(1–)

d. tris(2,2-bipyridine)nickel(II) nitrate or tris(2,2-bipyridine)nickel(2+) nitrate (The

e. hexacarbonylmolybdenum(0) (also commonly called “molybdenum hexacarbonyl”).

9.4 a. tetraamminecopper(II) or tetraamminecopper(2+)

e. nonahydridorhenate(VII) or nonahydridorhenate(2–) (This ion is commonly called

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9.5 a. triamminetrichloroplatinum(IV) or triamminetrichloroplatinum(1+)

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ONO OH2 ONO I

ONO OH2 ONO OH2

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9.8 a. triammineaquadichlorocobalt(III) chloride Isomers are of the cation:

H3N Cl H3N OH2 H2O NH3

H3N NH3 NH3 NH3

c. potassium diaquabis(oxalato)manganate(III) Isomers are of the anion:

H2O OH2 H2O

cis enantiomers trans

b. diaquadiiododinitritopalladium(IV) H2O ONO

Cl NH3 H3N NH3

H 2O NH3 H 2O NH3 Cl OH2 Cl OH2

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H 3N Br H 2O NH3 Br OH2 Cl OH2

OH2 Br NH3 NH3

H 2O NH3 H 3N OH2 H2 O NH3 H3 N OH2

OH2 OH2 OH2

Cl OH2 I OH2 Cl OH2

cis enantiomers trans

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h. Re(arphos)2Br2 Abbreviating the bidentate ligands As P :

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9.16 a, b. Abbreviating the bidentate ligands N P and O S :

9.17 The single C–N stretching frequency indicates a trans

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NH3 NH3 OH2 OH2 Br Br

P OH2 H2O P P NH3 H3 N P P OH2 H 2O P

NH3 NH3 OH2 OH2 Br Br

NH3 NH3 OH2 OH2 NH3 NH3

9.21 20b  20c top ring: , bottom ring: 

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right-handed (PR) propellers. If two P(mesityl)3 phosphines are attached in a CH3

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The representation  reduces to 2 A1 + 2 E + A2 + ECollectively these representations

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9.29 a. Cu(acacCN)2: D2h tpt: C2v

MOF Surface Area ( m2 g ) Accessible Pore Volume ( cm3 g )

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Amine-functionalized Mg 2 (dobpdc) was prepared by mixing H 4 (dobpdc) , magnesium bromide,

The metallation options include premetallation and postmetallation. In premetallation,

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Wagner, Jacob, i. 236.

X. Y. Z. affair, i. 355, 358, 359.

Yale College, i. 106.