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Published January 12, 2009 | Supplemental Material
Journal Article Open

Elucidation of heterocumulene activation by a nucleophilic-at-metal iridium(I) carbene


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.

Additional Information

© 2009 American Chemical Society. Received October 9, 2008. Publication Date (Web): November 24, 2008. We gratefully acknowledge the Moore Foundation (fellowship to M.T.W.) and BP (MC2 program) for financial support. Larry Henling provided crystallographic assistance, and Dr. Ian Stewart aided with DFT calculations. Supporting Information: Calculated surfaces and energies for frontier molecular orbitals of 1, 3, 5, and 6. Crystallographic details for complexes 4, 5, 6, and 8 are provided in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.

Attached Files

Supplemental Material - WHIo08.cif

Supplemental Material - WHIo08supp.pdf


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