Reactivity of [2,6-bis((dimethylamino)methyl)phenyl]gold(I), an unusual intermolecularly stabilized bis(amino)aryl-gold(I) dimer, toward alkyl halides, X-ray crystal structures of its iodomethane and methylene diiodide adducts

被引:18
作者
Contel, M
Nobel, D
Spek, AL
van Koten, G
机构
[1] Univ Utrecht, Debye Inst, Dept Met Mediated Synth, NL-3584 CH Utrecht, Netherlands
[2] Univ Utrecht, Bijvoet Ctr Biomol Res, Dept Crystal & Struct Chem, NL-3584 CH Utrecht, Netherlands
关键词
D O I
10.1021/om991043v
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Novel [2,6-bis((dimethylamino)methyl)phenyl]gold(I) dimer(4) was prepared in 60% yield from [AuCl(tht)] (tht = tetrahydrothiophene) and [2,6-bis((dimethylamino)methyl)phenyl]-lithium. Compound 4 is a rare example of a dimeric organogold(I) species involving intermolecular gold(I)-N(sp(3)) coordination. Variable-temperature NMR points to the formation of a 10-membered ring and provides evidence for the occurrence of a boat-chair ring conformation equilibrium. Reaction of 4 with Mel affords; the unexpected heteroaurate(I) [Au(C6H3{CH2NMe3}(2)-2,6)I]I (5) by Me transfer to the nitrogen atom of the ortho amino ligand. The molecular structure of 5 was elucidated by means of X-ray analysis. Conversely, the reaction of 4 with CH2I2 afforded the organogold(III) complex [Au(C6H3{CH2NMe2}-2-{CH2N(Me)(2)CH2}-6)I]I (6), containing a methylene fragment bridging a Au(III) center and a quaternary N center, as confirmed by a single-crystal X-ray diffraction study. A mechanistic pathway involving prior coordination of the alkyl halide to gold(I) followed by oxidative addition and alkyl transfer is proposed to account for the formation of both 5 and 6.
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页码:3288 / 3295
页数:8
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