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Published on: April 10, 2015
Isolation and reactivity of heteroleptic magnesium 1,3-benzazaphospholide complexes
1Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Zhejiang Key Laboratory of Organosilicon Material Technology, College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 311121, Zhejiang Province, China. cfpi@hznu.edu.cn.
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Reactions of 2,5-disubstituted-1H-1,3-benzazaphosphole (HBp) 1 [HBp1 (1a): R1 = Ph, R2 = Me; HBp2 (1b): R1 = Ph, R2 = H] with one equivalent of the β-diketiminate complex [CH{C(Me)NAr}2MgnBu] (Ar = 2,6-iPr2C6H3) [(DippBDI)MgnBu], respectively, produce in good yields low-coordinate magnesium compounds (DippBDI)Mg [κ1(N)-η3-Bp] 2 (Bp1(2a), Bp2(2b)), in which the ambident Bp- ligand coordinates to the magnesium centers through the Mg-N bond in both solution and solid phases. Compounds 2a and 2b can coordinate with THF to form four-coordinate magnesium 1,3-benzazaphospholides (DippBDI)Mg(THF)[κ1(N)-Bp] 3 (Bp1(3a), Bp2(3b)). 2a and 2b readily reacted with elemental sulfur to give new compounds (DippBDI)Mg(κ2(S,S)-BpS2) 4 (Bp1(4a), Bp2(4b)). Compounds 2a and 2b when treated with 2,2'-dipyridyl disulfide (PyS)2 afforded unexpected racemic axially restricted Bp(p)-(p)Bp rac-5 (Bp1(5a), Bp2(5b)). These new magnesium 1,3-benzazaphospholide complexes have been characterised by X-ray crystallography, except for 4b and rac-5b.
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