Dual reactivity pattern of Mn(I) carbyne complexes Cp(CO)2Mn+≡C–R (R = Ar, Alk) vs. dppm: Subtle balance between double intramolecular nucleophilic addition and nucleophilic addition followed by migratory CO insertion
作者:Dmitry A. Valyaev、Kamil I. Utegenov、Vassily V. Krivykh、Jérémy Willot、Nikolai A. Ustynyuk、Noël Lugan
DOI:10.1016/j.jorganchem.2017.12.029
日期:2018.7
The Mn(I) cationic carbyne complexes [Cp(CO)2Mn+≡C–R]BX4 (R = Ph, Tol, Me, Bn; X = F, Cl, Ph) react with bis(diphenylphosphino)methane to afford selectively either cyclic λ5-1,3-diphosphetium semi-ylides [RC–P+Ph2CH2P+Ph2)]BPh4 ([R4]BPh4; R = Ph, Tol), or Mn(I) complexes [Cp(CO)Mn(η3-(P,C,C)-Ph2PCH2P+Ph2C(R)=C=O)]BX4 ([R5]BX4; R = Me, X = Ph; R = Bn, X = F) featuring unprecedented phosphonioketene
Mn(I)阳离子碳炔络合物[Cp(CO)2 Mn + C–R] BX 4(R = Ph,Tol,Me,Bn; X = F,Cl,Ph)与双(二苯基膦基)甲烷反应生成得到选择性地或者环状λ 5 -1,3- diphosphetium半叶立德[RC-P +博士2 CH 2 P +博士2)] BPH 4([ - [R 4 ] BPH 4 ; R = PH,TOL),或Mn( I)配合物的[Cp(CO)的Mn(η 3 - (P,C,C)-Ph 2 PCH 2 P +博士2 C(R)= C = O)] BX 4([ - [R 5 ] BX4;R =我,X = Ph;R = Bn,X = F)的特征在于空前的膦基次甲基配体,分别取决于碳炔基取代基,芳基或烷基的性质。这些产品的选择性形成通过暂时形成带有悬垂膦部分的阳离子阳离子Mn(I)膦碳碳烯络合物[Cp(CO)2 Mn = C(R)PPh 2 + CH