Synthesis of a “Masked” Terminal Nickel(II) Sulfide by Reductive Deprotection and its Reaction with Nitrous Oxide |
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| Authors: | Nathaniel J Hartmann Dr Guang Wu Prof?Dr Trevor W Hayton |
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| Affiliation: | Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, CA 93106 (USA) |
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| Abstract: | The addition of 1 equiv of KSCPh3 to LRNiCl] (LR={(2,6‐iPr2C6H3)NC(R)}2CH; R=Me, tBu) in C6H6 results in the formation of LRNi(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 NiII sulfides, K(18‐crown‐6)]LRNi(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)]LtBuNi(SN?NO)], which features the first example of a thiohyponitrite (κ2‐SN?NO]2?) ligand. |
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| Keywords: | coordination chemistry nickel nitrogen oxides protecting groups sulfides |
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