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Synthesis and Exchange Reactions of Sulfur‐Rich Nickel and Palladium [M(L)(‘S 3 ’)] Complexes [‘S 3 ’ 2– = Bis(2‐mercaptophenyl)sulfide(2–)]
Author(s) -
Sellmann Dieter,
Geipel Franz,
Heinemann Frank W.
Publication year - 2000
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/(sici)1099-0682(200002)2000:2<271::aid-ejic271>3.0.co;2-m
Subject(s) - chemistry , nickel , palladium , sulfide , ligand (biochemistry) , bimetallic strip , nucleophile , medicinal chemistry , reactivity (psychology) , sulfur , stereochemistry , crystallography , metal , catalysis , organic chemistry , receptor , biochemistry , alternative medicine , pathology , medicine
In order to obtain suitable precursors for nickel and palladium complexes that model the reactivity of the active sites of hydrogenases and CO dehydrogenases, a series of [M(L)(‘S 3 ’)] complexes has been synthesized [M = Ni II , Pd II ; ‘S 3 ’ 2– = bis(2‐mercaptophenyl)sulfide(2–)]. X‐ray structure determinations of [Ni(‘S 3 ’)] 3 ( 1 ) and [Pd(‘S 3 ’)] 3 ( 2 ) have revealed that the [M(‘S 3 ’)] fragments trimerize to give six‐membered [MS] 3 rings, which exhibit chair conformations with alternating M II centers and thiolate bridging atoms. Reactions of the parent complex [Ni(‘S 3 ’)] 3 ( 1 ) with nucleophiles L, such as thiolates SR – (R = t Bu, Cy, Me, Ph), phosphanes PR 3 (R = Cy, Ph), chloride, or azide, have been found to yield the corresponding anionic or neutral [Ni(L)(‘S 3 ’)] complexes, which were isolated as (NBu 4 )[Ni(SR)(‘S 3 ’)] [R = t Bu ( 3 ), Cy ( 4 ), Me ( 5 ), Ph ( 6 )], [Ni(PR 3 )(‘S 3 ’)] [R = Cy ( 7 ), Ph ( 8 )], (NBu 4 )[Ni(Cl)(‘S 3 ’)] ( 9 ), and (NBu 4 )[Ni(N 3 )(‘S 3 ’)] ( 10 ). When treated with Me 3 SiX, the S t Bu – ligand in (NBu 4 )[Ni(S t Bu)(‘S 3 ’)] ( 3 ) was exchanged to give (NBu 4 )[Ni(X)(‘S 3 ’)] [X = Cl – ( 9 ), N 3 – ( 10 ), NCS – ( 11 ), NSO – ( 12 )]. The palladium complex [Pd(‘S 3 ’)] 3 ( 2 ) could also be cleaved with S t Bu – , but the resulting (NBu 4 )[Pd(S t Bu)(‘S 3 ’)] ( 13 ) proved inert towards exchange reactions with Me 3 SiX. All the mononuclear complexes have been characterized by standard spectroscopic techniques and by elemental analysis. The molecular structures of 3 , 4 , 6 , 7 , 8 , 9 , and 13 have been determined by X‐ray crystallography. The [MS 3 L] core geometries of all the complexes are non‐planar, exhibiting a considerable tetrahedral distortion.