Heterometallic Multiple Bonding: Delocalized Three-Center σ and π Bonding in Chains of 4d and 5d Transition Metals

• Published in: Inorganic chemistry Vol. 53; no. 21; pp. 11354 - 11356
• Main Authors: Brogden, David W, Berry, John F
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 03.11.2014
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic5024218

Heterotrimetallic compounds Mo2Ru(dpa)4Cl2 (1) and W2Ru(dpa)4Cl2 (2) are prepared by reactions of M2(dpa)4 (M = Mo or W; dpa = 2,2′-dipyridylamide) with [Ru(CO)3Cl2]2. Crystallographic studies reveal short Mo–Ru and W–Ru distances, 2.38 Å (1) and 2.39 Å (2), suggestive of delocalized Mo–Mo–Ru and W–W–Ru bonding. In contrast to the σ bonding found in the corresponding iron compounds, density functional theory calculations reveal both a three-center/two-electron σ bond and two three-center/four-electron π bonds in the M–M–Ru compounds.