Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 110. Synthesis of compounds with tungsten–copper or –gold bonds; crystal structure of [NEt4][W2Cu(µ-CCCBut)2(CO)4(η5-C2B9H9Me2)2]·Et2O
- 1 January 1991
- journal article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 3,p. 519-527
- https://doi.org/10.1039/dt9910000519
Abstract
Treatment of the reagents [NEt4][W(CR)(CO)2(η5-C2B9H9Me2)] in CH2Cl2 with 1 equivalent of CuCl or [AuCl(tht)](tht = tetrahydrothiophene) affords the labile complexes [NEt4][WMCl(µ-CR)(CO)2(η5-C2B9H9Me2)](M = Cu or Au, R = C6H4Me-4 or CCBut). Use of 2 equivalents of CuCl yields the stable tungstendicopper species [NEt4][WCu2Cl2(µ-CR)(CO)2(η5-C2B9H9Me2)], which may also be obtained by adding 1 equivalent of CuCl to the tungsten-copper dimetal compounds in CH2Cl2. Reactions of the salts [NEt4][WCuCl(µ-CR)(CO)2(η5-C2B9H9Me2)] with CNR′ in CH2Cl2 in the presence of TIBF4 yields the neutral complexes [WCu(µ-CR)(CO)2(CNR′)(η5-C2B9H9Me2)](R = C6H4Me-4 or CCBut, R′= C6H3Me2-2,6; R = CCBut, R′= But). The trimetal compounds [NEt4][W2M(µ-CR)2(CO)4(η5-C2B9H9Me2)2](M = Cu, R = C6H4Me-4 or CCBut; M = Au, R = CCBut) have been prepared by treating, in CH2Cl2, 2 equivalents of the reagents [NEt4][W(CR)(CO)2(η5-C2B9H9Me2)] with 1 equivalent of CuCl or [AuCl(tht)] in the presence of TIBF4. An X-ray diffraction study of the salt [NEt4][W2Cu(µ-CCCBut)2(CO)4(η5-C2B9H9Me2)2] revealed a novel structure in the crystal. The anion has a W2Cu spine [W–Cu 2.602(1) and 2.764(1)Å, W–Cu–W 152.7(1)°] with each metal–metal bond asymmetrically bridged by a CCCBut group [µ-C-W 1.85(1), µ-C-Cu(av.) 2.08(1)Å; W-µ-C-CCBut(av.) 169.5(1)°]. The shorter of the two W–Cu separations is also spanned by a C2B9H9Me2 cage. As expected the latter is η5 co-ordinated to the tungsten atom, but it also forms an exopolyhedral B–H Cu three-centre two-electron bridge bond employing the boron atom β to the carbon atoms in the pentagonal CCBBB face of the cage [µ-B–W 2.36(1), µ-B–Cu 2.33(1)Å]. The other tungsten atom is ligated by a C2B9H9Me2 group in the normal η5 bonding mode, and both tungstens carry two terminally bound CO groups. The reaction between [W(CCCBut)(CO)2(η-C5H5)] and [Pt(nb)3](nb = norbornene = bicyclo[2.2.1] heptene) affords the compound [W2Pt(µ-CCCBut)2(CO)4(η-C5H5)2]. The 1H and 13C-{1H} NMR data for the new compounds are reported and discussed.Keywords
This publication has 31 references indexed in Scilit:
- Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 100. Synthesis of mixed-metal compounds via the salts [NEt4][Rh(CO)L(η5-C2B9H9R2)](L = PPh3, R = H; L = CO, R = Me); crystal structures of the complexes [WRhAu(µ-CC6H4Me-4)(CO)3(PPh3)(η-C5H5)(η5-C2B9H11)] and [WRh2Au2(µ3-CC6H4Me-4)(CO)6(η-C5H5)(η5-C2B9H9Me2)2]·0.5CH2Cl2J. Chem. Soc., Dalton Trans., 1990
- Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 99. Synthesis of the cluster compounds [MWCoAu(µ-CC6H4Me-4)(µ3-CR)(CO)4(η-C5H5)(η-C5Me5)(η5-C2B9H9Me2)](M = Mo or W, R = C6H4Me-4; M = W, R = Me); crystal structure of the complex [MoWCoAu-(µ-CC6H4Me-4)(µ3-CC6H4Me-4)(CO)4(η-C5H5)(η-C5Me5)(η5-C2B9H9Me2)]·CH2Cl2J. Chem. Soc., Dalton Trans., 1990
- Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 98. Tri- and tetra-nuclear metal compounds with ethylidyne or p-tolylmethylidyne groups, and having both cyclopentadienyl and carbaborane ligandsJ. Chem. Soc., Dalton Trans., 1990
- Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 88. Carbaboranetungsteniridium compounds; crystal structure of the complex [WIr(µ-CC6H4Me-4)(CO)2(PEt3)2(η5-C2B9H9Me2)]J. Chem. Soc., Dalton Trans., 1989
- Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 84. Carbaborane tungsten–platinum complexes having a µ-CC6H3Me2-2,6 ligand; crystal structures of [WPt(µ-CC6H3Me2-2,6)(CO)n(PEt3)(µ-σ:η5-C2B9H8Me2)](n= 2 or 3)J. Chem. Soc., Dalton Trans., 1989
- Reconsideration of the crystal structure refinement of the complex [PPh4][W(CC6H4Me-4)(CO)2(η5-C2B9H9Me2)]J. Chem. Soc., Dalton Trans., 1988
- Cupracarboranes containing a closo-Cu(I)C2B9 geometry. Synthesis and structure of [(PPh3)CuC2B9H11]- and [(PPh3)2Cu2(.mu.-H)2C2B9H9]Inorganic Chemistry, 1987
- Syntheses of heterotetranuclear metallocarboranes containing a planar M2Cu2 (M = Mo, W) rhomb and B-H-Cu bridges: structure of [Mo2Cu2(.mu.-CO)4(CO)2(.mu.-H)2(C2B9H10)2]2-Journal of the American Chemical Society, 1987
- Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 67. Reactions of the salts [X][W(CR)(CO)2(η5-C2B9H9Me2)][X = P(CH2Ph)Ph3, R = C6H4Me-4; X = NEt4, R = Ph] with bis(cyclo-octa-1,5-diene)platinumJ. Chem. Soc., Dalton Trans., 1987
- Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 51. Alkylidyne(carbaborane)tungsten-gold and -rhodium complexes; crystal structures of [AuW(µ-CR)(CO)2(PPh3)(η-5C2B9H9Me2)], [RhW(µ-CR)(CO)2(PPh3)2(η5-C2B9H9Me2)], and (RhW[µ-CR)(CO)2(PPh3)2{η5-C2B9(C7H9)H8Me2}](R = C6H4Me-4)J. Chem. Soc., Dalton Trans., 1987