Reactions of hydroborating reagents with phosphinorhodium hydride complexes:: molecular structures of a Rh2B3 metallaborane cluster, an L2Rh(η2-H2BR2) complex and a mixed valence Rh dimer containing a semi-bridging Bcat (cat=1,2-O2C6H4) group

被引:72
作者
Westcott, SA
Marder, TB
Baker, RT
Harlow, RL
Calabrese, JC
Lam, KC
Lin, ZY
机构
[1] Mt Allison Univ, Dept Chem, Sackville, NB E4L 1G8, Canada
[2] Univ Durham, Dept Chem, Durham DH1 3LE, England
[3] Los Alamos Natl Lab, Chem Sci & Technol Div, Los Alamos, NM 87545 USA
[4] DuPont Co Inc, Expt Stn, Cent Res & Dev, Sci & Engn Labs, Wilmington, DE 19880 USA
[5] Hong Kong Univ Sci & Technol, Inst Mol Technol Drug Discovery & Synthesis, Dept Chem, Kowloon, Hong Kong, Peoples R China
[6] Hong Kong Univ Sci & Technol, Inst Mol Technol Drug Discovery & Synthesis, Open Lab Chirotechnol, Kowloon, Hong Kong, Peoples R China
关键词
rhodium hydrides; bridging boryls; catalyzed hydroborations;
D O I
10.1016/j.poly.2004.05.012
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The formation of products derived from competing reactions in Rh-catalyzed alkene hydroborations prompted us to study in situ interactions of several hydroborating reagents with unsaturated phosphinorhodium complexes. The reaction of [Rh(mu-H)(DiPPE)](2) (1) with borane-dimethylsulfide gave several rhodium-boron containing products including the structurally characterized metallaborane [RhH(DiPPE)](2)B3H7 (2) [DiPPE = 1,2-bis(diisopropylphosphino)ethane]. Addition of thexylborane and 9-H-BBN dimers, containing alkyl groups, to 1 gave the corresponding mononuclear substituted borohydride complexes Rh(eta(2)-H2BRR')(DiPPE) (4: R=H, R' = C(CH3)(2)CH(CH3)(2); 5: R,R'=bicyclo-[3.3.1]-nonane [C8H14]). The analogous monodentate phosphine complex Rh(eta(2)- H2BC8H14)(PPr'(3))(2) (6) was isolated and structurally characterized. Addition of catecholborane (HBcat; cat = 1,2-O2C6H4) to 1 gave the unusual dinuclear species Rh(DiPPE)(mu-H)(2)(mu-Bcat)RhH(DiPPE) (7) containing a semi-bridging Beat group, confirmed by single-crystal X-ray diffraction, and zwitterionic Rh(eta(6) -catBcat)(DiPPE) (8). Implications for rhodium-catalyzed hydroborations are addressed. (C) 2004 Elsevier Ltd. All rights reserved.
引用
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页码:2665 / 2677
页数:13
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