The Reaction of Molybdenum Pentachloride and Chloroxomolybdenum Complexes with Sodium Azide

Abstract

The reaction of MoC15 with NaN3 in acetonitrile followed by addition of OPPh3 resulted in the forma—tion of impure Mo0O13) (OPPh7)2 rather than the expected nitrido analogue. NaN3 acts here as a ,reducing agent generating a molybdenum(IV) chloride derivative which was trapped as impure Mo014(Py)2. The reaction of Mo0C14 with acetonitrile or NaN3 produced a green solution containing an Mo0017(MeON)2 complex which could not be isolated but trapped with OPPh3 and identified as Mo0C17(01Th3)2. Addition of NaN3 to the green molybdenum oxotrichloride intermediate, Mo0013(MeCN)2 produced a deep violet solution. The viole product could not be isolated but was inferred to consist of ENa][Mo0C135 (N.)(MeCN)J, a loose adduct of. Mo0C13(MeON)2 and NaN3. Thus, addition of OPPh3 to the violet solution resulted in the formation of impure Mo0013 (OPPh3)2. . The violet intermediate obtained from Mo0017(MeCN)2 and NaN3 is stable in acetonitrile but decomposes in CH2012 under evolution of N2 and reduction yielding Mo0012(MeON)3 as a brown crystalline product which is sensitive toihydrolysie. 1100015 (OPPh3)2 itself reacts y . slower with NaN3 in acetonitrile with chloride-azide exchange yielding Mo0012(N3)(OPPh3)2.