A dimolybdenum(III) azido compound: its decomposition into amido and nitrido derivatives. Crystal structure of [Mo 3(O)(N)Cp 3(SMe) 4]

• Published in: Journal of organometallic chemistry Vol. 560; no. 1; pp. 245 - 251
• Main Authors: Schollhammer, P, Pétillon, F.Y, Talarmin, J, Muir, Kenneth W
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15-06-1998
• Subjects: Amido ligand; Azido ligand; Chemical Sciences; Crystal structure; Cyclopentadienyl; Di- and trimolybdenum complex; Nitrido ligand; Thiolato-bridged complexes; Azido ligand; Cyclopentadienyl; Amido ligand; Di- and trimolybdenum complex; Thiolato-bridged complexes; Nitrido ligand; Crystal structure
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/S0022-328X(98)00516-6

The thermal reaction of [Mo
2Cp
2(
μ-SMe)
3(
μ-Cl)]
1 with NaN
3 in THF/EtOH gives a mixture of three compounds: [Mo
2Cp
2(
μ-SMe)
3(
μ-N
3)]
2, [Mo
2Cp
2(
μ-SMe)
3(
μ-NH
2)]
3 and [Mo
3(O)(N)Cp
3(SMe)
4]
4. Only the
μ-azido derivative
2 is isolated if the time of thermolysis is short. Its formation in the presence of EtOH leads in turn to the products
3 and
4. Production of
3 from
2 requires N
2 loss followed by intermolecular reduction of the bimetallic system. Complete decomposition of the complexes occurs if the time of reaction is prolonged. An X-ray diffraction study shows that
4 contains a [Mo
2Cp
2(
μ-SMe)
3(
μ-N)] core that is linked through a MoN double bond to a CpMo(O)(SMe) unit. The resulting Mo
3(
μ
3-N) fragment, in which the NMo double bond is supported by two MoN single bonds involving the directly bonded metal atoms, is the most striking structural feature of
4. The triply-bridging nitrido nitrogen atom adopts a distorted trigonal planar coordination.