Diene, Alkyne, Alkene, and Alkyl Complexes of Early Transition Metals: Structures and Synthetic Applications in Organic and Polymer Chemistry ye Yasuda* and Akira Nakamura* An unprecedented series of highly reactive alkene- and diene-complexes of the early transi tion metals (Groups 3A-5A of the periodic system) have been isolated recently. Diene com plexes of this sort (M=Ti, Zr, Hf, Nb, Ta) prefer, besides the (n'-s-cs-dieneymetal struc ture, either a novel bent y-metallacyclo-3-pentene structure or the unique (n*s-rans diene)metal structure. In bis(dienejmetal complexes of Nb and Ta the ns-cis-dienes a sume an unusual exo-endo ¢supine-prone) geometry. The M-C bonds in these diene-metal Complexes generally exhibit highly polarized o-bonding along with x-bonding character. The complexes therefore undergo a variety of regio- and stereoselective carbomet sith substrates containing C-C, C-O, or C-N multiple bonds. Examples of the products that can be obtained include ketones, viny] ketones, unsaturated primary, secondary, and tertiary alcohols, as well as diols and unsaturated acids. Mechanistic studies on the sti chiometric and catalytic conversions of unsaturated hydrocarbons provides, inter alia, some insights into the course of polymerization reactions. 1. Introduction Organic compounds of the early transition metals (groups 3A-SA of the periodic system) are currently at tracting considerable attention because oftheir fascinating structural features, their mode of M-C bonding, and their unusually high selectivity in carbometalations: all these features distinguish them from the conventional middle and late transition metal complexes. The recent acceler: ated development of alkene-metal chemistry in this area is largely a consequence of the successful isolation of highly reactive novel species with suitable auxiliary ligands, espe- cially cyclopentadienyl (Cp) and pentamethyleyclopenta dienyl (Cp*) ligands. The first part of this article is con cemed with new aspects of the structural chemistry of diene, alkene-, and alkyne- as well as allyl and pentadie rnyl-metal complexes of the early transition metals, while the second part deals with the unusual C-C coupling reac: tions that have been accomplished with these complexes. For an overview of the organometallic chemistry of the early transition metals in its entirety, the reader should consult some of the excellent monographs" and reviews ‘on alkylmetal compounds. carbene-complexes,"! and me: tallacyeles!! that are available. 2. Remarkable Structural Features of Diene, ‘Alkene, and Alkyne Complexes of the Early Transition Metals 2.1, Structures of n*Metallacyclo-3-pentene- and int-etrans-Diene-Metal Complexes Conjugated dienes, typified by 1.3-butidiene, may coor dinate to a metal in several ways, The relative contribution YP rH Yasuds, Prof De A Naka of each of the limiting structures 1-6 would appear to de ‘pend upon the ligands of the metal and the substituents of the diene. The vast majority of middle and late transition metalsdiene complexes assume the conventional (ns-it~ 13ediene) structure 1 or the (J.2-n/-s-rans-1.-diene) structure 6, where the diene interacts with Fe, Ru, Rh. Mo, Mo ete. via alkene rjorbitals" It is now apparent from pe oly onl “} X-ray and NMR data that the diene complexes of early ition metals of groups 4A (Ti,"! Zr!" HP") and SA, Tike those of group 3A (U.!"! Th), prefer the bent (o°,x-bonded)y'-metallacyclo-3-pentene structure 2, the planar (a"-bondedyy-metallacyclo-3-pen tene structure 3 oF the novel (n!-s-trans-diene}metal struc ture’, Unequivacal evidence for the structure of type § still lacking, Differentiation of the n/-structure 6 from its ‘o-bonded counterpart (2-vinylmetallacyclopropane) seems improbable on the basis of the prediction made by Dewar ‘et a). although the latter geometry is well known in 2-vinylphosphiranes. Typical synthetic routes to these diene complexes involve the use of dienemagnesium rea gents or of pentadieny! anions," the chemical or photo chemical reduction of the corresponding precursor com plex in the presence of the diene." metal stom vapor techniques rearrangements of transitory diviny! com plexes!" or hydride elimination from allylmetal com. pounds or metallacycles!"" As typical example of such a (© VCH Verogigeeicha mbt, D-H Weimeim, IT aSToaNAI A? asnKI7295 U2 50.) 723day AnIn) H. Yasuda Ke Matuoks,K.Nagasuna, A. Nakamura, unpaid fe] H. Yat. B,Alta, A, Nahar, emp (85) aC MeDase JE Beraw. J Organeme. Chom 27¥(1948) 281-6) Eiken fer Chem Re. 17984 FON} X MDevot 6. M. Wh U8 H. nade. T: Okamoto H. Yamamoto, A. Nakamura, Shlabe 28 (97) DF Brauer C. Kroger, Orgamamotalis 13982) 207 8] K Jona. Wc. 2. Neto BIN ISAS 1113, (91 T Olam, A Yasuda, T Ata A. Nekamets, S2nd Anne Mee Chom Sic fp 1986 Abse IR, {WY KAUN, Kania, K Miki. Kes, K Mashima, K. Nagsona Hanada, A» Nakamra, Che La 192. 199: 8). Skibbe, © (01) 15 Jone J L Petersen, J Am Chem. So, 108 (988 580: 9B I ast ec GAR Eg Reh (62) a) Takaaki, DA Swanion, E.Nephi, Chm Lat 1987. 623°) Kiringu) H.Teuben, 1 Organomer Chem. 1199) 3 183) Yasuda, A, Nakamura, Ree Chem. Ferme 6 (106) 365, [24] FW Jolly G. Wilke: The Orne Chomuny of Nee. Academic (85141 G Henpcr Ole. S Ohne Anger: Chem. #7 U9T5) 11 Ange 'usceldine, AG. 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Durand, F Dawane Tse J Pali Sot A 19709999 {i2t a)G Nats Le Por: Plimer Chemin of Site Elaiome. ni: 12M 416" Nata, LsPorts A. Muzze D. Morera, Chin nd Atlan 10251... Papi eri Morea Ch. Pd Aon 4 120 1G. eer, Ker lena G Schroth, Chem: Ber 118 3985) 1385 {1A sees of 2ec pall ndenel comple st abe aalale by eae fon oF ZC pCMaene wih alapneniem lide eer (8). 1M. Kamach,N- Waban © Mutahesh Movants "18 IDS G, Eker, K. Engel V. Routh, P Cash Berke, PCaubee R.Van ree: Orgnomeratin #1088 153 [126 478A Delgo. £1 Tnyatou. L$ H. Guzman, LL Atma snore J, Poti Ser oii Chom. E29 84 1st 4G. Nata Part Corrs, G. Zan, F Campi J Plrmer So) 811198) HET] 2) Ls, PP Chi Id lan S197 186) Po Mali: Marat Chom. 77 1741S [12m 4 Forskana, R Hil M. Nakamura, Pim. SB 166) 67 U3 2) R Gin, RH. Groby ton Chom So 11886) 730 by L Cluwetn. J Soto, SL Buchnald, ML Stgerald, RH. Gris lu 2) TA Kata $1 Lee J de, Cem, Soe 2098042: 69 7. Kae URI) ML HL Gren, Be Appl Chom $0,197 27 Ange. Cher Int Ed. gh 24,1987) 724-749