by X-ray crystallography. The crystals are monoclinic, space group P21/n; refinement gave R = 0.053 for 2593 reflections with I ⩾ 2.5σ(I). The reaction of the complex fac-[O3ClOMn(CO)3(dppm)] with Ph2PCH2CH2Cl in Cl2CH2 gives the salt fac-[Mn(CO)3(dppm)(Ph2PCH2CH2Cl)]ClO4 which isomerizes to mer-[Mn(CO)3(dppm)(Ph2PCH2CH2Cl)]ClO4 in boiling butanol. Both cationic carbonyl complexes give the acyl species
膦Ph 2 PCH 2 CH 2 Cl与fac- [XMn(CO)3(dppm)](X = Cl或Br)在回流的
甲苯中反应,生成配合物顺式,顺式-[XMn(CO)2(dppm) (Ph 2 PCH 2 CH 2 Cl)](I)。用THF中的Na
汞齐处理这些物质,得到烷基络合物[Ph 2 n(CO)2(dppm)](II),该化合物在正常条件下不与CO反应,但可以转化为顺式,顺式-[ClMn (CO)2(dppm)(PPh 2[Et)]与HCl(g)在
乙醚中反应。如果在CO存在下用Na / Hg还原I,则得到化合物顺式-[Ph 2 n(CO)2(dppm)](III)。后者也可以直接从fac- [BrMn(CO)3(dppm)],Ph 2 PCH 2 CH 2 Cl和Na / Hg在THF中制备,并通过X射线晶体学表征。晶体为单斜晶体,空间群为P 2 1 / n。细化,得到[R = 0.053对于2593个反射与我⩾2