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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Hybrid dibismuthines and distibines as ligands towards transition metal carbonyls
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Hybrid dibismuthines and distibines as ligands towards transition metal carbonyls

机译：杂二双变蛋白和Distibines作为过渡金属羰基的配体

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摘要

The hybrid dibismuthines O(CH_2CH_2BiPh _2)_2 and MeN(CH_2-2-C_6H _4BiPh_2)_2 react with [M(CO)_5(thf)] (M = Cr or W) to form [{M(CO)_5}_2{O(CH_2CH _2BiPh_2)_2}] and [{Cr(CO)_5} _2{MeN(CH_2-2-C_6H_4BiPh _2)_2}] containing bridging bidentate (Bi_2) coordination. The unsymmetrical tertiary bismuthine complexes [M(CO) _5{BiPh_2(o-C_6H_4OMe)}] are also described. Depending upon the molar ratio, the hybrid distibines O(CH _2CH_2SbMe_2)_2 and MeN(CH _2-2-C_6H_4SbMe_2)_2 react with [M(CO)_5(thf)] to give the pentacarbonyl complexes [{M(CO) _5}_2{O(CH_2CH_2SbMe_2) _2}] and [{Cr(CO)_5}_2{MeN(CH_2-2-C _6H_4SbMe_2)_2}] or tetracarbonyls cis-[M(CO)_4{O(CH_2CH_2SbMe_2) _2}] and cis-[M(CO)_4{MeN(CH_2-2-C _6H_4SbMe_2)_2}]. The latter can also be obtained from [Cr(CO)_4(nbd)] or [W(CO)_4(pip) _2], and contain chelating bidentates (Sb_2-coordinated) as determined crystallographically. S(CH_2-2-C_6H _4SbMe_2)_2 coordinates as a tridentate (SSb _2) in fac-[M(CO)_3{S(CH_2-2-C_6H _4SbMe_2)_2}] (M = Cr or Mo) and fac-[Mn(CO) _3{S(CH_2-2-C_6H_4SbMe_2) _2}][CF_3SO_3]. Fac-[Mn(CO) _3{MeN(CH_2-2-C_6H_4SbMe _2)_2}][CF_3SO_3] contains NSb _2-coordinated ligand in the solid state, but in solution a second species, Sb_2-coordinated and with a κ1-CF _3SO_3 replacing the coordinated amine is also evident. X-ray crystal structures were also determined for fac-[Cr(CO) _3{S(CH_2-2-C_6H_4SbMe_2) _2}], fac-[Mn(CO)_3{S(CH_2-2-C_6H _4SbMe_2)_2}][CF_3SO_3] and fac-[Mn(CO)_3{MeN(CH_2-2-C_6H_4SbMe _2)_2}] [CF_3SO_3]. Hypervalent N?Sb interactions are present in cis-[M(CO)_4{MeN(CH _2-2-C_6H_4SbMe_2)_2}] (M = Mo or W), but absent for M = Cr.
机译：杂二双变蛋白O（CH_2CH_2BiPh _2）_2和MeN（CH_2-2-C_6H _4BiPh_2）_2与[M（CO）_5（thf）]（M = Cr或W）反应形成[{M（CO）_5} _2 {O（CH_2CH _2BiPh_2）_2}]和[{Cr（CO）_5} _2 {MeN（CH_2-2-C_6H_4BiPh _2）_2}}包含桥联双齿（Bi_2）配合。还描述了不对称的叔铋配合物[M（CO）_5 {BiPh_2（o-C_6H_4OMe）}。取决于摩尔比，杂化双歧物O（CH _2CH_2SbMe_2）_2和MeN（CH _2-2-C_6H_4SbMe_2）_2与[M（CO）_5（thf）]反应生成五羰基配合物[{M（CO）_5 } _2 {O（CH_2CH_2SbMe_2）_2}]和[{Cr（CO）_5} _2 {MeN（CH_2-2-C _6H_4SbMe_2）_2}]或四羰基顺式[[M（CO）_4 {O（CH_2CH_2SbMe_2）_2} ]和cis- [M（CO）_4 {MeN（CH_2-2-C _6H_4SbMe_2）_2}]。后者也可以从[Cr（CO）_4（nbd）]或[W（CO）_4（pip）_2]中获得，并且含有晶体学确定的螯合双齿（Sb_2配位）。 S（CH_2-2-C_6H _4SbMe_2）_2在fac- [M（CO）_3 {S（CH_2-2-C_6H _4SbMe_2）_2}]（M = Cr或Mo）和fac-中作为三齿（SSb _2）坐标[Mn（CO）_3 {S（CH_2-2-C_6H_4SbMe_2）_2}] [CF_3SO_3]。 Fac- [Mn（CO）_3 {MeN（CH_2-2-C_6H_4SbMe _2）_2}] [CF_3SO_3]包含固态的NSb _2配体，但在溶液中包含第二种Sb_2配位且具有κ1- CF _3SO_3取代配位胺也很明显。还确定了fac- [Cr（CO）_3 {S（CH_2-2-C_6H_4SbMe_2）_2}]，fac- [Mn（CO）_3 {S（CH_2-2-C_6H _4SbMe_2）_2}的X射线晶体结构] [CF_3SO_3]和fac- [Mn（CO）_3 {MeN（CH_2-2-C_6H_4SbMe _2）_2}] [CF_3SO_3]。顺式[M（CO）_4 {MeN（CH _2-2-C_6H_4SbMe_2）_2}]（M = Mo或W）中存在超价N2Sb相互作用，但M = Cr则不存在。

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