取代环戊二烯基三羰基合铬(钼)卤化物η~5-RC_5H_4(CO)_3MX的合成及结构

Synthesis and Structures of Substituted Cyclopen-tadienylchromium(molybdenum)tricarbonyl Halides η5-RC_5H_4(CO)_3MX

由η~5-RC_5H_4(CO)_3MNa(1)(R=MeCO,MeO_2C,EtO_2C;M=Cr,Mo)与 I_2、三卤化磷(PX(?),X=Cl,Br,I)、苯基二氯化膦或甲基二碘化胂反应,可得金属卤化物η~5-RCH_4(CO)_3MX(2a—21)(M=Cr,X=I;M=Mo,X=Cl,Br,I).鉴于1(R=MeO_2C,M=Mo)与 PCl_3反应的中间物η~5-MeO_2CC_5H_4(CO)_3MoPCl_2业已被析离,并可转变为相应氯化物η~5-MeO_2CC_5H_4(CO)_3MoCl(2g),因此1与三卤化磷、苯基二卤化膦或甲基二碘化胂生成金属卤化物的反应很可能经缩合及中间物分解两步简单反应.2f(R=MeCO,M=Mo,X=I)为单斜晶系,a=0.6663(2),b=1.2364(6),c=1.5464(5)nm;β=99.02(3)°;V=1.2581nm^3;D_o=2.186g/cm^3;Z=4;F(000)=776;空间群P2_1/c.

Organometallic halides with formula of η~5-RC_5H_4(CO)_3MX 2a—2c (R=MeCO,MeO_2C,EtO_2C;M=Cr;X=I),2d—21(R=MeCO,MeO_2C,EtO_2C;M=Mo;X=Cl,Br,I)have been prepared by the reactions of RC_5H_4(CO)_3MNa(1) with I_2,phosphorustrihalides PX_3(X=Cl,Br,I),phenyl dichlorophosphine,or methyl diiodoarsine.Thereactions of 1 with phosphorus trihalides,phenyl dichlorophosphine or methyldiiodoarsine proceed most likely via two simple steps:the condensation followed bydecomposition of the intermediates,since the intermediate MeO_2CC_5H_4(CO)_3MoPCl_2 hasbeen isolated during the reaction of 1 (R=MeO_2C,M=Mo) with PCl_3 and it can beconverted to MeO_2CC_5H_4 (CO)_3MoCl (2g).The crystals of 2f (R=MeCO,M=Mo,X=I)belong to monoclinic system a=0.6663(2),b=1.2364(6),c=1.5464(5) nm;β=99.02(3)°;V=1.2581 nm^3;Dc=2.186 g/cm^3;Z=4;F(000)=776;space group P2_1/c.