Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published January 12, 2009 | Supplemental Material
Journal Article Open

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

Abstract

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

Files

WHIo08supp.pdf
Files (853.1 kB)
Name Size Download all
md5:7a19e85f1232a72870abcb1233ffec30
100.7 kB Download
md5:13a5655406e4752ebb6780227a8a8bb3
752.4 kB Preview Download

Additional details

Created:
August 22, 2023
Modified:
October 17, 2023