Rhodium pincer complexes of 2,2′-bis(diphenylphosphino)diphenylamine

被引:71
作者
Winter, AM
Eichele, K
Mack, HG
Potuznik, S
Mayer, HA
Kaska, WC
机构
[1] Univ Tubingen, Inst Anorgan Chem, D-72076 Tubingen, Germany
[2] Univ Tubingen, Inst Phys & Theoret Chem, D-72076 Tubingen, Germany
[3] Univ Calif Santa Barbara, Dept Chem, Santa Barbara, CA 93106 USA
关键词
PNP pincer ligand; rhodium complexes; N-H oxidative addition; quantum chemical calculations;
D O I
10.1016/S0022-328X(03)00776-9
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The novel pincer ligand 2,2'-bis(diphenylphosphino)diphenylamine (1) has been synthesized by treatment of 2,2'-dibromodiphenylamine with n-butyl lithium and subsequent reaction with diphenylchlorophosphine. When ligand 1 is treated with RhCl3 hydrate the dinuclear complex la forms which can be converted into the square planar carbonyl complex 1c upon reduction with Na/Hg in the presence of CO. Depending on the reaction conditions two different complexes were isolated when 1 reacts with [(COE)(2)RhCl](2). In THF the hydrochloro complex 1b and with n-butyl lithium the COE complex Id is generated. Interestingly, the formation of 1b represents a rare case of N-H oxidative addition to a late transition metal complex fragment. Compound 1c is observed upon reaction of the COE complex Id with carbon monoxide. Quantum chemical calculations at different levels of theory are in good agreement with the experimental structure of 1c. (C) 2003 Elsevier B.V. All rights reserved.
引用
收藏
页码:149 / 154
页数:6
相关论文
共 32 条
[1]  
Albrecht M, 2001, ANGEW CHEM INT EDIT, V40, P3750, DOI 10.1002/1521-3773(20011015)40:20<3750::AID-ANIE3750>3.0.CO
[2]  
2-6
[3]   Bonding and stereochemistry of three-coordinated transition metal compounds [J].
Alvarez, S .
COORDINATION CHEMISTRY REVIEWS, 1999, 193-5 :13-41
[4]   DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
BECKE, AD .
PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100
[5]   Using soluble polymers to recover catalysts and ligands [J].
Bergbreiter, DE .
CHEMICAL REVIEWS, 2002, 102 (10) :3345-3383
[6]   Phosphinoalkylsilyl complexes.: 12.: Stereochemistry of the tridentate bis(diphenylphosphinopropyl)silyl (biPSi) framework:: Complexation that introduces "face discrimination" at coordinatively unsaturated metal centers.: X-ray crystal and molecular structures of Pt[SiMe(CH2CH2CH2PPh2)2]Cl, IrH[SiMe(CH2CH2CH2PPh2)2]Cl, and RuH[SiMe(CH2CH2CH2PPh2)2](CO)2 [J].
Brost, RD ;
Bruce, GC ;
Joslin, FL ;
Stobart, SR .
ORGANOMETALLICS, 1997, 16 (26) :5669-5680
[7]   MONOMERIC METAL-HYDROXIDES, ALKOXIDES, AND AMIDES OF THE LATE TRANSITION-METALS - SYNTHESIS, REACTIONS, AND THERMOCHEMISTRY [J].
BRYNDZA, HE ;
TAM, W .
CHEMICAL REVIEWS, 1988, 88 (07) :1163-1188
[8]   The use of ultra- and nanofiltration techniques in homogeneous catalyst recycling [J].
Dijkstra, HP ;
Van Klink, GPM ;
Van Koten, G .
ACCOUNTS OF CHEMICAL RESEARCH, 2002, 35 (09) :798-810
[9]   3 COORDINATION IN METAL-COMPLEXES [J].
ELLER, PG ;
BRADLEY, DC ;
HURSTHOUSE, MB ;
MEEK, DW .
COORDINATION CHEMISTRY REVIEWS, 1977, 24 (01) :1-95
[10]   Chelating amides of lithium. Synthesis, structure and coordination chemistry [J].
Fryzuk, MD ;
Giesbrecht, GR ;
Johnson, SA ;
Kickham, JE ;
Love, JB .
POLYHEDRON, 1998, 17 (5-6) :947-952