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Nickel‐Molybdenum and Nickel‐Tungsten Dithiolates: Hybrid Models for Hydrogenases and Hydrodesulfurization
Author(s) -
Schilter David,
Fuller Amy L.,
Gray Danielle L.
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500740
Subject(s) - chemistry , nickel , molybdenum , hydride , catalysis , conjugate , medicinal chemistry , metal , tungsten , hydrogenase , inorganic chemistry , organic chemistry , mathematical analysis , mathematics
The heterobimetallic complexes [(dppe)Ni(pdt)Mo(CO) 4 ], [(dcpe)Ni(pdt)Mo(CO) 4 ], [(dppe)Ni(pdt)W(CO) 4 ] and [(dcpe)Ni(pdt)W(CO) 4 ] {dppe = Ph 2 P(CH 2 ) 2 PPh 2 ; dcpe = Cy 2 P(CH 2 ) 2 PCy 2 ; pdt 2– = – S(CH 2 ) 3 S – } have been prepared and structurally characterized. The internuclear separation in these Ni II M 0 species is highly sensitive to diphosphine basicity and is smallest in the dppe complexes wherein the planar Ni centres are electron‐poor and require interaction with the group 6 metal. The Ni II W 0 species [(dppe)Ni(pdt)W(CO) 4 ] was converted into its stable conjugate acid [(dppe)Ni(pdt)HW(CO) 4 ] + , a rare example of a nickel–tungsten hydride. This Ni II HW II complex is an electrocatalyst for H + reduction and is relevant to both biological and synthetic H 2 ‐processing catalysts.