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In Pursuit of the Molybdenum(III) Tris(thiolate) Fragment:  Unusual Structure of a Dimolybdenum μ-Nitrido Complex

Agapie, Theodor and Odom, Aaron L. and Cummins, Christopher C. (2000) In Pursuit of the Molybdenum(III) Tris(thiolate) Fragment:  Unusual Structure of a Dimolybdenum μ-Nitrido Complex. Inorganic Chemistry, 39 (2). pp. 174-179. ISSN 0020-1669. doi:10.1021/ic9904891.

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The new molybdenum nitrido−thiolate complex N⋮Mo(SAd)_3 (Ad = 1-adamantyl) was prepared by a ligand exchange route involving reaction of Ti(SAd)(O^(i)Pr)_3 with Chisholm's nitrido−butoxide complex N⋮Mo(O^(t)Bu)_3. In an effort to abstract the nitrido nitrogen from N⋮Mo(SAd)_3, the compound was treated with Mo(N[^(t)Bu]Ph)_3, a three-coordinate molybdenum(III) complex. This resulted in formation of the unusual and thermally unstable (μ-nitrido)dimolybdenum complex (AdS)_3Mo(μ-N)Mo(N[^(t)Bu]Ph)_3, which was isolated and characterized. An X-ray study revealed (AdS)_3Mo(μ-N)Mo(N[^(t)Bu]Ph)_3 to possess an unsymmetrical Mo−(μ-N)−Mo linkage, the Mo−thiolate fragment exhibiting a substantially longer bond to the bridging nitrogen atom. The structure of (AdS)_3Mo(μ-N)Mo(N[^(t)Bu]Ph)_3 is noteworthy, displaying trigonal monopyramidal coordination at the (μ-N)−Mo−thiolate Mo center. Since N⋮Mo(N[^(t)Bu]Ph)_3 is a good leaving group, (AdS)_3Mo(μ-N)Mo(N[^(t)Bu]Ph)_3 should be a source of the reactive Mo(SAd)_3 fragment. In all the studied reactions of the (μ-nitrido)dimolybdenum complex one of the observed products was N⋮Mo(N[^(t)Bu]Ph)_3. Two products containing the Mo(SAd)_3 fragment were observed:  (AdS)_3Mo⋮Mo(SAd)_3 and [(ON)Mo(μ-SAd)(SAd)_2]_2. Upon treatment with pyridine, the tris(thio-1-adamantyl)(nitrosyl)molybdenum dimer forms the pyridine adduct (AdS)_3Mo(NO)(py), which is a monomer.

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Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2000 American Chemical Society. Received May 6, 1999. For funding, C.C.C. is grateful to the National Science Fundation (CAREER Award CHE-9501992), the Alfred P. Sloan Foundation, and the Packard Foundation. T.A. thanks MIT’s UROP (Undergraduate Research Opportunities Program) for funding. T.A. is grateful to Daniel J. Mindiola for instructive guidance in single crystal X-ray structure analysis. T.A. also thanks Jane R. Brock and Yi-Chou Tsai for helpful discussions. The authors are grateful to Prof. Luis M. Baraldo for CV measurements.
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Alfred P. Sloan FoundationUNSPECIFIED
David and Lucile Packard FoundationUNSPECIFIED
Massachusetts Institute of Technology (MIT)UNSPECIFIED
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ID Code:90659
Deposited By: Donna Wrublewski
Deposited On:06 Nov 2018 17:09
Last Modified:16 Nov 2021 03:34

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