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

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Abstract
The new molybdenum nitrido-thiolate complex N drop Mo(SAd)(3) (Ad = 1-adamantyl) was prepared by a ligand exchange route involving reaction of Ti(SAd)((OPr)-Pr-i)(3) with Chisholm's nitrido-butoxide complex N drop Mo((OBu)-Bu-t)(3). In an effort to abstract the nitrido nitrogen from N drop Mo(SAd)(3), the compound was treated with Mo(N[Bu-t]Ph)(3), a three-coordinate molybdenum(III) complex. This resulted in formation of the unusual and thermally unstable (mu-nitrido)dimolybdenum complex (AdS)(3)Mo(mu-N)Mo(N[Bu-t]Ph)(3), which was isolated and characterized. An X-ray study revealed (AdS)(3)Mo(mu-N)Mo(N[tBu]Ph)3 to possess an unsymmetrical Mo-(mu-N)-Mo linkage, the Mo-thiolate fragment exhibiting a substantially longer bond to the bridging nitrogen atom. The structure of (AdS)(3)Mo-(mu-N)Mo(N[Bu-t]Ph)(3) is noteworthy, displaying trigonal monopyramidal coordination at the (mu-N)-Mo-thiolate Mo center. Since N drop Mo(N[Bu-t]Ph)(3) is a good leaving group, (AdS)(3)Mo(mu-N)Mo(N[Bu-t]Ph)(3) should be a source of the reactive Mo(SAd)(3) fragment. In all the studied reactions of the (mu-nitrido)dimolybdenum complex one of the observed products was N drop Mo([Bu-t]Ph)(3). Two products containing the Mo(SAd)(3) fragment were observed: (AdS)(3)Mo drop Mo(SAd)(3) and [(ON)Mo(mu-SAd)(SAd)(2)](2). Upon treatment with pyridine, the tris(thio-1-adamantyl)(nitrosyl)molybdenum dimer forms the pyridine adduct (AdS)(3)Mo(NO)(py), which is a monomer.

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