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Highly Soluble Sulfur‐Rich [Ni(L)( si S 3 )] Complexes Containing the New Ligand Bis(2‐mercapto‐3‐trimethylsilylphenyl) Sulfide(2−) ( si S 3 2− )
Author(s) -
Sellmann Dieter,
Prakash Raju,
Geipel Franz,
Heinemann Frank W.
Publication year - 2002
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 - 10.1002/1099-0682(200208)2002:8<2138::aid-ejic2138>3.0.co;2-h
Subject(s) - chemistry , sulfur , crystallography , stereochemistry , sulfide , organic chemistry
The new organosulfur ligands si S 3 ‐H 2 [ si S 3 2− = bis(2‐mercapto‐3‐trimethylsilylphenyl) sulfide(2−)] and ca S 3 ‐H 2 [ ca S 3 2− = bis(2‐mercapto‐3‐carboxyphenyl) sulfide(2−)] were synthesized from H S 3 ‐H 2 [ H S 3 2− = bis(2‐mercaptophenyl) sulfide(2−)], n ‐butyllithium, and Me 3 SiCl or CO 2 /H + . Reaction of si S 3 ‐H 2 with Ni(ac) 2 ·4H 2 O gave the air‐stable and well‐soluble trinuclear complex [Ni( si S 3 )] 3 ( 1 ) whose structure was determined by X‐ray crystallography. Reactions of complex 1 with nucleophiles L [L = PR 3 (R = n Pr, Ph, Cy), N 2 H 4 , S t Bu − , and Cl − ] yielded the corresponding neutral or anionic complexes, which were isolated as [Ni(PR 3 )( si S 3 )] [R = n Pr ( 2 ), Ph ( 3 ), Cy ( 4 )], Bu 4 N[Ni(Cl)( si S 3 )] ( 5 ), Bu 4 N[Ni(S t Bu)( si S 3 )] ( 6 ), and [Ni(N 2 H 4 )( si S 3 )] ( 8 ). The azido complex Et 4 N[Ni(N 3 )( si S 3 )] ( 7 ) was prepared from Me 3 SiN 3 and the precursor chloro complex Et 4 N[Ni(Cl)( si S 3 )]. Reaction of 1 with NH 3 yielded labile [Ni(NH 3 )( si S 3 )] ( 9 ), which was characterized in solution by 1 H and 13 C NMR spectroscopy. Analogously, 1 reacts with nicotinamide (NA) or diethylnicotinamide (NAEt 2 ) to give, from equilibrium reactions, the corresponding mononuclear [Ni(L)( si S 3 )] complexes with L = NA, NAEt 2 . X‐ray structure determinations showed that 1 , 3 , 4 , 5 , and 7 all exhibit tetrahedrally distorted planar [Ni(L)( si S 3 )] fragments. Complex 7 is the first structurally characterized azidonickel complex with a coligand having exclusively sulfur donors. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)