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Synthesis of a "Masked" Terminal Nickel(II) Sulfide by Reductive Deprotection and its Reaction with Nitrous Oxide.

ABSTRACT: The addition of 1?equiv of KSCPh3 to [L(R)NiCl] (L(R) = {(2,6-iPr2C6H3)NC(R)}2CH; R = Me, tBu) in C6H6 results in the formation of [L(R)Ni(SCPh3)] (1: R = Me; 2: R = tBu) in good yields. Subsequent reduction of 1 and 2 with 2?equiv of KC8 in cold (-25?°C) Et2O in the presence of 2?equiv of 18-crown-6 results in the formation of "masked" terminal Ni(II) sulfides, [K(18-crown-6)][L(R)Ni(S)] (3: R = Me; 4: R = tBu), also in good yields. An X-ray crystallographic analysis of these complexes suggests that they feature partial multiple-bond character in their Ni-S linkages. Addition of N2O to a toluene solution of 4 provides [K(18-crown-6)][L(tBu)Ni(SN=NO)], which features the first example of a thiohyponitrite (?(2)-[SN=NO](2-)) ligand.

SUBMITTER: Hartmann NJ

PROVIDER: S-EPMC4715500 | biostudies-literature | 2015 Dec

REPOSITORIES: biostudies-literature

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Synthesis of a "Masked" Terminal Nickel(II) Sulfide by Reductive Deprotection and its Reaction with Nitrous Oxide.

Hartmann Nathaniel J NJ Wu Guang G Hayton Trevor W TW

Angewandte Chemie (International ed. in English) 20151012 49

The addition of 1 equiv of KSCPh3 to [L(R)NiCl] (L(R) = {(2,6-iPr2C6H3)NC(R)}2CH; R = Me, tBu) in C6H6 results in the formation of [L(R)Ni(SCPh3)] (1: R = Me; 2: R = tBu) in good yields. Subsequent reduction of 1 and 2 with 2 equiv of KC8 in cold (-25 °C) Et2O in the presence of 2 equiv of 18-crown-6 results in the formation of "masked" terminal Ni(II) sulfides, [K(18-crown-6)][L(R)Ni(S)] (3: R = Me; 4: R = tBu), also in good yields. An X-ray crystallographic analysis of these complexes suggests ...[more]

PMID: 26457792

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