钌和锇的二氢双（甲巯咪唑基）硼酸盐配合物

Dihydrobis(methimazolyl)borato complexes of ruthenium and osmium.

作者信息

Foreman Mark R St-J, Ma Chenxi, Hill Anthony F, Otten Natalie E, Sharma Manab, Tshabang Never, Ward Jas S

机构信息

Research School of Chemistry, Australian National University, Acton, Canberra, A.C.T., Australia.

出版信息

Dalton Trans. 2017 Nov 7;46(43):14957-14972. doi: 10.1039/c7dt02420g.

DOI:10.1039/c7dt02420g

PMID:29044261

Abstract

The reaction of Na[HB(mt)] (mt = 2-mercapto, 3-methylimidazol-1-yl, methimazolyl) with [Ru(X)Cl(CO)(PPh)] (n = 3 X = H; n = 2 BOCH, SiCl, SiMe) affords the complexes [Ru(X)(CO)(PPh){κ-H,S,S'-HB(mt)}]. Evidence is presented to also support the transient formation of [Ru(X)(CO)(PPh){κ-H,S,S'-HB(mt)}] (X = CH[double bond, length as m-dash]CHPh, Ph) via a similar strategy, although these are unstable. The osmium complex [OsH(CO)(PPh){κ-H,S,S'-HB(mt)}] is similarly obtained from [OsHCl(CO)(PPh)] or [OsH(NCMe)(CO)(PPh)]BF. The reaction of [RuH(CO)(PPh){κ-H,S,S'-HB(mt)}] with chloroform or diphenyldiselenide provides [Ru(X)(CO)(PPh){κ-H,S,S'-HB(mt)}] (X = Cl, SePh), the latter reaction also providing traces of [Ru(SeH)(CO)(PPh){κ-H,S,S'-HB(mt)}]. Spectroscopic and structural data for the series [Ru(X)(CO)(PPh){κ-H,S,S'-HB(mt)}] are discussed in terms of perturbations on the B-H-Ru interaction by the trans-ligand X.

摘要

Na[HB(mt)]（mt = 2 - 巯基，3 - 甲基咪唑 - 1 - 基，甲硫咪唑基）与[Ru(X)Cl(CO)(PPh)]（n = 3，X = H；n = 2，BOCH，SiCl，SiMe）反应得到配合物[Ru(X)(CO)(PPh){κ - H,S,S'-HB(mt)}]。有证据表明，通过类似策略也能短暂形成[Ru(X)(CO)(PPh){κ - H,S,S'-HB(mt)}]（X = CH[双键，长度为m破折号]CHPh，Ph），尽管这些不稳定。锇配合物[OsH(CO)(PPh){κ - H,S,S'-HB(mt)}]同样由[OsHCl(CO)(PPh)]或[OsH(NCMe)(CO)(PPh)]BF制得。[RuH(CO)(PPh){κ - H,S,S'-HB(mt)}]与氯仿或二苯基二硒醚反应生成[Ru(X)(CO)(PPh){κ - H,S,S'-HB(mt)}]（X = Cl，SePh），后一反应还生成痕量的[Ru(SeH)(CO)(PPh){κ - H,S,S'-HB(mt)}]。针对系列[Ru(X)(CO)(PPh){κ - H,S,S'-HB(mt)}]的光谱和结构数据，根据反位配体X对B - H - Ru相互作用的扰动进行了讨论。