Flexible Coordination of Diphosphine Ligands Leading to cis and trans Pd(0), Pd(II), and Rh(I) Complexes

被引：27
|
作者：
Comanescu, Cezar C. [1 ]
Iluc, Vlad M. [1 ]
机构：
[1] Univ Notre Dame, Dept Chem & Biochem, Notre Dame, IN 46556 USA
来源：
INORGANIC CHEMISTRY | 2014年 / 53卷 / 16期
基金：
美国国家科学基金会;
关键词：
METAL-COMPLEXES; C-H; AGOSTIC INTERACTIONS; CHIRAL DIPHOSPHINE; HECK REACTIONS; PALLADIUM; ACTIVATION; CATALYSIS; BACKBONE; PD;
D O I：
10.1021/ic5010566
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
A series of diphosphine ligands (Pr2P)-Pr-i-C6H4-X-C6H4-(PPr2)-Pr-i (for ligand L-1, X = CH2; for ligand L-2, X = CH2CH2) was investigated to determine the preference for cis/trans coordination to palladium(0), palladium(11), and rhodium(I). Increasing the length of the bridging alkyl backbone from one to two carbons changes the geometry of the resulting palladium(II) complexes, with L-1 coordinating preferentially cis, while L-2 coordinates in a trans fashion. Coordination to Pd(0) leads to (LPd)-Pd-1(dba) and (LPd)-Pd-2(dba), in which both ligands accommodate a P-M-P angle close to 120 degrees. L-2 was found to coordinate cis in a rhodium(I) complex ([(LRh)-Rh-2(nbd)][BF4], where nbd = norbornadiene).
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页码：8517 / 8528
页数：12
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