1,2-Halogenverschiebung in cymantrenacetylen-komplexen

Use of the MnCC system in organometallic and organic synthesis

“…The irreversible reduction is typical of complexes Cp(CO) 2 MnM(-C CHPh)(LL ) (37,(52)(53)(54)(55)(56)(57), where L, L = PPh 3 , P(OR) 3 , CO. More stable Cp(CO) 2 MnM(-C CHPh)(P-P) (P-P = dppe, dppp) (59, 60, 64, 65) are reduced reversibly. The reduction of Cp(CO) 2 MnPt(-C CHPh)(dppm) (58) is quasi-reversible and proceeds more easily (−2.37 V) than Cp(CO) 2 MnPt(-C CHPh)(P-P) (P-P = dppe (59), dppp (60)) (−2.54 V) [137].…”

“…Complexes ( 5 -C 5 H 4 R)(CO) 2 (17), was structurally characterized [57]. The analogous -complexes with chloro-or bromopropyne-acetals were not subjected to AVR.…”

Metal Vinylidenes and Allenylidenes in Catalysis: Applications in Anti‐Markovnikov Additions to Terminal Alkynes and Alkene Metathesis

“…[29,30] Internal alkynes bearing a labile substituent are also prone to form vinylidene derivatives. Trialkylsilyl, [31][32][33][34][35][36][37] alkylthiol, [38] triphenylstannane, [39] and iodide [40,41] are able to migrate and generate functionalized vinylidene metal complexes, and some of them have been involved in catalytic reactions.…”

Manganese Hydrocarbon Complexes Excluding Cyclopentadienyl

“…76 Similar reactions utilizing the reduction of bis(r| 5 -cyclopentadienyl)manganese provide an improved method for the preparation of carbonyl-free organomanganese 7i-complexes. 76 The formation of (r| 2 -alkyne)manganese complexes also is most often accomplished by substitution of a labile ligand such as tetrahydrofuran 77 ' 78 or ethyl ether, 79 as is demonstrated by the preparation of T| 2 -alkyne complex (117) starting from Cp(CO) 2 Mn(THF) (Scheme 13). 77 Reaction of (117) with phenyllithium followed by protonation generates the manganese vinylidene complex (118), a rearrangement which has also been demonstrated with (l-iodo-rj 2 -alkyne)manganese complexes.…”

“…77 Reaction of (117) with phenyllithium followed by protonation generates the manganese vinylidene complex (118), a rearrangement which has also been demonstrated with (l-iodo-rj 2 -alkyne)manganese complexes. 79 The reaction of amines with (r| 2 -acetylene)manganese complex (119) provides a useful approach to aminocarbene complexes (120) (Equation (20) …”