Reactions of Ru-alkynyl Complexes with Electrophilic Boranes

被引:14
作者
Boone, Michael P. [1 ]
Stephan, Douglas W. [1 ]
机构
[1] Univ Toronto, Toronto, ON, Canada
基金
加拿大自然科学与工程研究理事会;
关键词
FRUSTRATED LEWIS PAIRS; CYCLOPENTADIENYL-OSMIUM CHEMISTRY; METAL VINYLIDENES; ORGANOMETALLIC CHEMISTRY; ADDITION-REACTIONS; TERMINAL ALKYNES; RUTHENIUM; ACID; 1,1-CARBOBORATION; ZIRCONOCENES;
D O I
10.1021/om200815s
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The species CpRu(PPh3)(2)(C CPh) (1) reacts with HB(C6F5)(2) to effect the hydroboration of the metal-bound alkyne, giving the orange species CpRu(PPh3)(2)CH=C(Ph)(B(C6F5)(2)) (2) in 95% isolated yield. Subsequent photolysis of this species results in the rearrangement of the vinyl group to give the species CpRu(PPh3)[PhC C(B(H)(C6F5)(2))] (3) in 87% yield. The species exhibits a side-on alkyne donation to Ru as well as a bridging BH fragment. Intermediates in this conversion are discussed in relation to known species, and support for a transient zwitterionic intermediate is offered by the isolation of 1 CpRu(PPh3)(2)(C=CPh(C6F4)BF(C6F5)(2)) (4) from the reaction of CpRu-(PPh3)(2)(C CPh) with B(C6F5)(3). The compounds 2-4 are crystallographically characterized.
引用
收藏
页码:5537 / 5542
页数:6
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