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Synthesis

More On Multiple Bonding

October 28, 2013 | A version of this story appeared in Volume 91, Issue 43

The Science & Technology Concentrate about a new metal-metal bond didn’t mention the seminal contributions of James Collman, a professor at Stanford University (C&EN, Sept. 2, page 43). Between 1980 and 2000, the Collman lab synthesized and studied a unique series of metalloporphyrin complexes containing unsupported multiple bonds between metals of the second and third transition series.

This work allowed, for the first time, a systematic study of physical properties of heterometallic bonds, uncomplicated by bridging or labile ligands, varying charge, or low symmetry. The Collman group was the first to measure the barrier of rotation around the quadruple bond (Proc. Natl. Acad. Sci. USA , 2592), the first to prepare and study high-order bonds between metals of different triads (Inorg. Chem. 1999, DOI: 10.1021/ic9810337; Angew. Chem. Int. Ed.1271), and the first to exploit a subtle balance between the steric repulsion of the ligands and the steric requirements of the delta bond to control the overall geometry of the complex (Inorg. Chem. 1999, DOI: 10.1021/ie981032e).

Roman Boulatov
Liverpool

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