The preparation, structure, and reactions of the mononuclear thiolate–hydride complexes [MoH(SR)(dppe)2](R = bulky alkyl or aryl group, dppe = Ph2PCH2CH2PPh2); X-ray structure determination of cis-[MoH(SC6H2Pri3-2,4,6)(dppe)2]

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Abstract
Reaction of trans-[Mo(N2)2(dppe)2](dppe = Ph2PCH2CH2PPh2) with the bulky thiols RSH (R = Pri, But, C6H2Me3-2,4,6, C6H2Pri 3-2,4,6, or C6H2BrPri 2-4,2,6) at reflux in tetrahydrofuran (thf) gives the green hydride complexes [MoH(SR)(dppe)2]. The complex cis-[MoH(SC6H2Pri 3-2,4,6)(dppe)2]·0.5C6H5Me has a distorted octahedral structure, with distances: Mo–S 2.402(2), Mo–H 1.61(9), Mo–P 2.380(2)–2.465(2)Å. The 1H hydride resonances of these compounds occur in the range –3.98 to –4.98 p.p.m. (relative to SiMe4) and show fluxionality at room temperature with respect to the phosphorus atoms except for R = C6H2BrPri 2-4,2,6. Other spectroscopic properties of the compounds are used as a basis to discuss the mechanism of their formation. The complex [MoH(SC6H2Pri 3-2,4,6)(dppe)2] reacts at 20 °C with CO or ButNC to give the known compounds [Mo(CO)2(dppe)2] and [Mo(ButNC)2(dppe)2], and with PhSH to give trans-[Mo(SPh)2(dppe)2].

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