SYNTHESIS AND ELECTROPHILIC REACTIVITY OF [(ETA(5)-1-N(CH2CH2O)3SI-6-ME-C6H5)MN(CO)2NO]BF4

[{eta5-1-N(CH2CH2O)3Si-6-Me-C6H5}Mn(CO)2NO]BF4 [3(CO)] has been synthesized by the reaction of [{eta5-1-N(CH2CH2O)3Si-6-Me-C6H5}Mn(CO)3] (2) with NOBF4. The addition of phosphines or phosphite to 3(CO) yielded [{eta5-1-N-(CH2CH2O)3Si-6-Me-C6H5}Mn(CO)(L)NO]BF4 [3(L)] (L = PPh3, PMePh2, PHPh2, and P(OPh)3). Addition of excess P(OMe)3 to 3(CO) led to [{eta4-1-N(CH2CH2O)3Si-5-P(O)(OMe)2-6-Me-C6H5}-Mn(CO)2NO]' (4), which decomposed to liberate the 1,3-cyclohexadiene derivative of silatrane 5. Hydride addition to 3(CO) gave [{eta4-1-N(CH2CH2O)3Si-6-Me-C6H6}Mn(CO)2No] (6) and [{eta4-6-Me-5-N(CH2CH2O)3Si-C6H6}Mn(CO)2NO] (7). After removal of the manganese moiety from 6 and 7, 1,3-cyclohexadiene derivatives of silatrane, 8 and 10, were obtained. Treatment of 3(CO) with the carbanion of ethyl cyanoacetate and then Me3NO in refluxing benzene gave the cis-disubstituted cyclohexadiene derivative of silatrane, 12. Addition of LiCH2CN to 3(CO) yielded [{eta5-1-N(CH2CH2O)3Si-6-Me-C6H5}Mn(CO)?? {C(O)CH2CN}NO] [13(C(O)CH2CN)] which rearranged to the diene complex, presumably possessing an endo substituent. The diene compound afforded the trans-disubstituted cyclohexadiene derivative of silatrane 15(C(O)CH2CN), LiCH2CO2 (i)Pr, and LiCH2CO2 (t)Bu also attacked the CO in 3(CO), ultimately affording 15 (C(O)CH2CO2(i)Pr) and 15(C(O)CH2CO2(t)Bu), respectively.