Generation of vinylcarbyne complexes from reaction of the propynyl complex [Cp(CO)(PPh[sub 3])MnC[triple bond]CMe][sup [minus]] with aldehydes and ketones

Journal Article · Wed Sep 01 04:00:00 EDT 1993 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00033a037· OSTI ID:5577117

Terry, M R; Kelley, C; Lugan, N; Geoffroy, G L ^[1]; Haggerty, B S; Rheingold, A L ^[2]

---

1. Pennsylvania State Univ., University Park, PA (United States)
2. Univ. of Delaware, Newark, DE (United States)

The highly nucleophilic propynyl complex Li[sup +]Cp(CO)(PPh[sub 3])MnC[triple bond]CMe[sup [minus]] (2) reacts with a variety of aldehydes and ketones in the presence of BF[sub 3]-Et[sub 2]O to give, after quenching with MeOH, a series of cationic vinylcarbyne complexes of the general form [Cp(CO)(PPh[sub 3])Mn[triple bond]CC(Me)=C(R)(R[prime])]BF[sub 4] . The reactions of the R, R[prime] = Ph derivative with a series of nucleophiles (LiAlH[sub 4], RMgX, Bu[sup t]C[triple bond]CLi) have been studied, and addition occurs to both the [alpha]-carbon of the vinylcarbyne ligand to form vinylcarbene complexes [Cp(CO)(PPh[sub 3])Mn=C(R)C(Me)=CPh[sub 2]] (R = H, Me, Et, [minus]C[triple bond]CBu[sup t]) and to the [gamma]-carbon to give vinylidene complexes, with addition to C[sub [alpha]] being electronically preferred but with addition to C[sub [gamma]] being favored sterically because of the bulky PPh[sub 3] ligand. The vinylcarbyne complexes that have an acidic proton on the C[sub [gamma]] substituent undergo facile deprotonation to give vinylvinylidene derivatives of the general form Cp(CO)(PPh[sub 3])Mn=C=C(Me)C(R)=C(R[prime])[sub 2] (R[prime] = H, R = p-Tol Bu[sup t]; R[prime] = Me, R = H). The propynyl complex 2 also adds to the [gamma]-carbon of 5a to form the binuclear bis(vinylidene) complex [Cp(CO)(PPh[sub 3])Mn=C=C(Me)-][sub 2][C(Ph)[sub 2]] as a separable mixture of diastereomers. 17 refs., 3 figs., 4 tabs.

• OSTI ID: 5577117
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 12:9; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALDEHYDES
ALKYNES
CARBENES
CARBONYLS
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
HYDROCARBONS
KETONES
LIGANDS
LITHIUM COMPLEXES
MANGANESE COMPLEXES
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RADICALS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES