Synthesis and reactivity of the silylated triphosphites [(R1O)2PO]3SiR2(R1= Me or Et; R2= Me, Ph or CHCH2). Crystal structure of fac-[Mo(CO)3{P,P,P-[P(OMe)2O]3SiMe}]
摘要:
The silylated triphosphites [(R1O)2PO]3SiR2 (R1 = Me or Et; R2 =Me, Ph or CH=CH2) have been prepared in high yield by the reactions between SiR2Cl3 and (R1O)2P(=O)H in the presence of NEt3. The compound [(MeO)2PO]3SiMe reacts with [Mo(CO)4(nbd)] (nbd = norbornadiene) and [Mo(CO)3(eta6-C7H8)] to afford [Mo(CO)4{P,P-[P(OMe)2O]2SiMe[OP(OMe)2]}] and fac-[Mo(CO)3{P,P,P-[P(OMe)2O]3SiMe}] respectively. The crystal structure of fac-[Mo(CO)3{P,P,P-[P(OMe)2O]3SiMe}] has been determined in the space group P2(1)/c with a = 10.1 129(8), b = 14.3197(12) and c = 14.9906(11) angstrom. The metal-coordinated triphosphites are significantly less electron-releasing than tertiary phosphine analogues and more closely resemble the eta-arenes of [Mo(CO)3(eta6-C6H6-nMen)] in their electronic character.