Transition metal complexes of the chelating phosphine borane ligand Ph2PCH2Ph2P•BH3

被引:63
作者
Merle, N [1 ]
Koicok-Köhn, G [1 ]
Mahon, MF [1 ]
Frost, CG [1 ]
Ruggerio, GD [1 ]
Weller, AS [1 ]
Willis, MC [1 ]
机构
[1] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England
关键词
D O I
10.1039/b413650k
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Chromium and ruthenium complexes of the chelating phosphine borane H3B . dppm are reported. Addition of H3B . dppm to [Cr(CO)(4)(nbd)] (nbd = norbornadiene) affords [Cr(CO)(4)(eta(1)- H3B . dppm)] in which the borane is linked to the metal through a single B - H - Cr interaction. Addition of H3B . dppm to [CpRu(PR3)(NCMe)(2)](+) (Cp = eta(5)-C5H5) results in [CpRu(PR3)(eta(1)- H3B . dppm)][PF6] (R= Me, OMe) which also show a single B - H - Ru interaction. Reaction with [CpRu(NCMe)(3)](+) only resulted in a mixture of products. In contrast, with [Cp* Ru(NCMe)(3)](+) (Cp* = eta(5)-C5Me5) a single product is isolated in high yield: [Cp* Ru(eta(2)-H3B . dppm)][PF6]. This complex shows two B - H - Ru interactions. Reaction with L = PMe3 or CO breaks one of these and the complexes [Cp* Ru(L)(eta(1)- H3B . dppm)][PF6] are formed in good yield. With L = MeCN an equilibrium is established between [Cp* Ru(eta(2)-H3B . dppm)][PF6] and the acetonitrile adduct. [Cp* Ru(eta(2)-H3B . dppm)][PF6] can be considered as being "operationally unsaturated", effectively acting as a source of 16-electron [Cp* Ru(eta(1)- H3B . dppm)][PF6]. All the new compounds ( apart from the CO and MeCN adducts) have been characterised by X-ray crystallography. The solid-state structure of H3B . dppm is also reported.
引用
收藏
页码:3883 / 3892
页数:10
相关论文
共 67 条
[1]  
Albright T.A., 1985, ORBITAL INTERACTIONS
[2]  
ALDRIDGE S, 2001, CHEM COMMUN, P1986
[3]   Reactions with electrophiles control isomerization from η5(π)- to η1(P)-coordination of phosphinyl-substituted benzophospholide ligands [J].
Bajko, Z ;
Daniels, J ;
Gudat, D ;
Häp, S ;
Nieger, M .
ORGANOMETALLICS, 2002, 21 (24) :5182-5189
[4]   REACTIONS OF ORGANORUTHENIUM PHOSPHINE COMPLEXES WITH HYDROBORATING REAGENTS [J].
BAKER, RT ;
CALABRESE, JC ;
WESTCOTT, SA ;
MARDER, TB .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (34) :8777-8784
[5]   Novel T-shaped 14-electron platinum(II) complexes stabilized by one agostic interaction [J].
Baratta, W ;
Stoccoro, S ;
Doppiu, A ;
Herdtweck, E ;
Zucca, A ;
Rigo, P .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (01) :105-108
[6]   TRANSITION-METAL COMPLEXES OF 7-MEMBERED RING SYSTEMS .4. PROTON RESONANCE SPECTRA OF CYCLOHEPTATRIENE COMPLEXES OF GROUP VI METALS [J].
BENNETT, MA ;
WILKINSON, G ;
PRATT, L .
JOURNAL OF THE CHEMICAL SOCIETY, 1961, (MAY) :2037-+
[7]  
Braunschweig H, 1998, ANGEW CHEM INT EDIT, V37, P1786, DOI 10.1002/(SICI)1521-3773(19980803)37:13/14<1786::AID-ANIE1786>3.0.CO
[8]  
2-C
[9]  
BROOKHART M, 1988, PROG INORG CHEM, V36, P1
[10]   ADDITION-COMPOUNDS OF ALKALI-METAL HYDRIDES .20. REACTION OF REPRESENTATIVE MONO-ALKYLBORANES AND DIALKYLBORANES WITH SALINE HYDRIDES TO FORM THE CORRESPONDING ALKYLBOROHYDRIDES [J].
BROWN, HC ;
SINGARAM, B ;
MATHEW, CP .
JOURNAL OF ORGANIC CHEMISTRY, 1981, 46 (13) :2712-2717