Synthesis and Reactivity of (Phenylsilatrane)manganese Tricarbonyl Perchlorate: Molecular Structure of [{η⁵-1-N(CH₂CH₂0)₃Si-6-PhC₆H₅)Mn(CO)₃]

[{N(CH₂CH₂0)₃SiC₆H₅)Mn(CO)₃]ClO₄ (1) undergoes regioselective reaction with RMgBr (R = Ph, Me, Et) in CH₂C1₂ to give [η⁵-l-(N(CH₂CH₂O)₃Si)-6-(R)C₆H5]Mn(CO)3 (2a, R = Ph; 2b, R - Me; 2c, R - Et), with EtLi in THF to yield [η₅⁶-2-(N(CH₂CH₂0)₃Si)-6-(R)C₆H₆]Mn(CO)₃ (3c, R = Et), and with RMgBr (R = Ph, Me, Et), LiCH₂CO₂CMe₃, LiCH₂CN, and LiCHS(CH₂)₃S in THF to yield [η⁵-3-(N-(CH₂CH₂O)₃Si)-6-(R)C₆H₅]Mn(CO)₃ (4a, R = Ph; 4b, R = Me; 4c, R = Et; 4e, R = CH₂CO₂CMe₃; 4j, R = CH₂CN; 4k, R = CHS(CH₂)₃S). However, 1 does not react regioselectively with the carbanions from isobutyronitrile, acetone, or tert-butyllithium or with sodium cyanide. The selectivity of the nucleophilic addition to 1 is strongly dependent on the nucleophile and reaction medium. The structure of 2a has been confirmed by X-ray diffraction: space group PĪ; a = 9.169 (2) Å, b = 9.905 (2) Å, c = 12.353 Å, α = 110.25 (2)°, β = 97.33 (1)°, γ = 97.70 (2)°; final error indices R = 0.042, R_G = 0.043 for 2856 unique data with I > 3σ(I).