期刊
ORGANOMETALLICS
卷 28, 期 1, 页码 161-166出版社
AMER CHEMICAL SOC
DOI: 10.1021/om8009766
关键词
-
资金
- Moore Foundation
A carbene complex supported by the (PNP)Ir framework is shown to facilitate sulfur-atom transfer from CS2 and PhNCS by an unusual multiple-bond metathesis pathway, and kinetically trapped intermediates are provided to support the proposed metal-initiated mechanism for heterocumulene activation. Experimental and theoretical studies on a series of (PNP)Ir-L complexes suggest that a high-lying, nucleophilic Ir(dg) orbital mediates this unique reactivity. The combination of evidence indicates that square-planar Ir(I) carbenes of this type are best formulated as nucleophilic-at-metal carbenes, exhibiting reactivity initiated by a nucleophilic metal center rather than a nucleophilic or electrophilic carbene and providing products that are complementary to those typically observed for high-valent alkylidenes.
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