Addition, Cycloaddition, and Metathesis Reactions of the Cationic Carbyne Complexes [Cp(CO)2Mn.tplbond.CCH2R]+ and Neutral Vinylidene Complexes Cp(CO)2M:C:C(H)R (M = Mn, Re)

Metal-Assisted Cycloaddition Reactions in Organotransition Metal Chemistry

“…eq 67). While the carbonyl group in 55 is not attacked by DPNI, the CdN bond of tropone-imine complexes 241 readily reacts with DPNI to give cycloadducts 242, which after decomplexation undergo sigmatropic rearrangement to give 243 and 244, which latter are also A very interesting "criss-cross" reaction between benzalazine and the CdCH 2 double bond of the in situ formed vinylidene complexes 245a,b has been described by Geoffroy et al, 165,180 cf. eq 68.…”

“…The vinylidenerhenium complex 83, or its manganese analogue, adds its CdCH 2 double bond across the CdN double bond in PhNdCHPh 165,180 (Scheme 12) to give the carbene complex 84. This is analogous to the above mentioned cycloaddition of imines with vinylidene iron complexes.…”

Use of the MnCC system in organometallic and organic synthesis

“…Complex 61 is less stable than Cp(CO) 2 MnPt(-C CHPh)(PPh 3 ) 2 (52). Reactions between 61 and P-P = dppe, dppp led to quite stable complexes The reaction (28) between 61 and dppm gave two unstable compounds Cp(CO) 2 MnPd(-C CHPh)(PPh 3 )( 1 -dppm) (62) and Cp(CO) 2 MnPd(-C CHPh)( 2 -dppm) (63) [99].…”

“…They were stabilized in statu nascendi converting into [Cp(CO) 2 Mn] 2 (-C CH 2 ) (10) [50] and [Cp (CO) 2 Mn] 2 (-C CH 2 ) [51], respectively. Complex 9 can be observed in solution at −50 • C [52]. The only mononuclear manganese complex with the parent vinylidene stable at RT is (Me 3 SiC C)Mn C CH 2 (dmpe) 2 (11), synthesized by Berke and co-workers [53].…”

Addition of N-aryl imines to alkyne(pentacarbonyl)chromium and tungsten — a novel route to alkenyl(amino)carbene complexes

“…Analogously, several vinylidene complexes have been shown to readily add imines to the C C bond to form four-membered transition-metal-substituted N-heterocycles (Scheme 1). Examples include the formation of 2-azetidin-1-ylidene complexes from [Cp(CO)(L)Fe C CR 2 ] + [L=P(OMe) 3 , PPh 3 ; R=H, Me] and MeN C(H)aryl or thiazolines [2,3], from vinylidene complexes of manganese and rhenium and imines [4], and from [(CO) 5 W C CPh 2 ] and imines [5]. In general, oxidative decomplexation of the four-membered ring yields b-lactams in moderate to good yields.…”