多硅基取代π-苯基羰基钼化合物的合成和结构

Synthesis and Molecular Structure of Polysilanyl-substituted η~6-Phenylcarbonylmolybdenum

芳基二硅烷RC6H4 SiMe2 SiMe3 与Mo(CO) 3 Py3 在BF3 存在下反应 ,生成π 苯基羰基钼化合物 (η6 RC6H4 SiMe2 SiMe3 )Mo (CO) 3 (R =p Me和p OMe) .在同样条件下 ,二芳基二硅烷RC6H4 SiMe2 SiMe2 C6H4 R与两倍摩尔的Mo(CO) 3 Py3 反应 ,得到双钼化合物 (η6,η6 RC6H4 SiMe2 SiMe2 C6H4 R) [Mo(CO) 3 ] 2 和单钼化合物 (η6 RC6H4 SiMe2 SiMe2 C6H4 R)Mo(CO) 3 (R =H ,o Me ,m Me ,p Me和p OMe) .不对称二芳基二硅烷R1C6H4 SiMe2 SiMe2 C6H4 R2 进行上述反应 ,得到类似的化合物 (η6,η6 R1C6H4 SiMe2 SiMe2 C6H4 R2 ) [Mo(CO) 3 ] 2 和 (η R1C6H4 SiMe2 SiMe2 C6H4 R2 )Mo(CO) 3 (R1,R2 =H ,p Me和p OMe ;R1≠R2 ) .该单核化合物是由钼原子配位于不同苯基的异构体组成的混合物 .利用IR ,1HNMR和元素分析鉴定了所有产物 ,并利用单晶X射线衍射法对化合物 (η6,η6 RC6H4 SiMe2 SiMe2 C6H4 R) [Mo(CO) 3 ] 2 (R =p Me)的分子结构进行了测定 .

Aryldisilane RC 6H 4SiMe 2SiMe 3 reacted with Mo(CO) 3Py 3 in the presence of BF 3, giving (η 6-benzene)tricarbonylmolybdenum complex (η 6-RC 6H 4SiMe 2SiMe 3)Mo(CO) 3 ( R=H, p-Me and p-OMe). Under the same condition, diaryldisilane RC 6H 4SiMe 2SiMe 2C 6H 4R reacted with two equivalents of Mo(CO) 3Py 3 to afford di-molybdenum complex (η 6,η 6-RC 6H 4~SiMe 2~SiMe 2C 6~H 4R) 2 as well as mono-molybdenum complex (η 6-RC 6H 4SiMe 2SiMe 2C 6H 4R)Mo(CO) 3 ( R=H, o-Me, m-Me, p-Me and p-OMe). Unsymmetric diaryldisilane R 1C 6H 4SiMe 2SiMe 2C 6H 4R 2 underwent the above reaction to produce similarly the complexes (η 6,η 6-R 1~C 6~H 4~SiMe 2~SiMe 2~C 6H 4~R 2) 2 and (η 6-R 1~C 6H 4~Si^Me 2~SiMe 2~C 6H 4R 2)Mo(CO) 3 (R 1, R 2=H, p-Me and p-OMe; R 1≠R 2). This mononuclear complex was a mixture of isomers with molybdenum coordinated to different phenyl groups. All complexes obtained were characterized by elemental analyses, IR and 1H NMR spectra. The molecular structure of (η 6-RC 6H 4SiMe 2SiMe 2C 6H 4R) 2 (R=p-Me) has been determined by means of X-ray diffraction analysis.