TY - JOUR
T1 - Reactions of M(CO)5X (M = Mn, Re; X = Cl, Br) with {Ph2PCH2}3CCH3 (P3) and {Ph2P(CH2)2}3P (P3P')
T2 - Synthetic, spectroscopic, electrochemical, and electrospray mass spectrometric studies
AU - Bond, A. M.
AU - Colton, R.
AU - Van den Bergen, A.
AU - Walter, J. N.
PY - 2000/10/16
Y1 - 2000/10/16
N2 - The reactions of M(CO)5X (M = Mn, Re; X = Cl, Br) with {Ph2PCH2}3CCH3 (P3) and {Ph2P(CH2)2}3P (P3P') are investigated, and the products are characterized by IR, NMR (31P and 13C), and electrospray mass spectrometric (ESMS) techniques. With P3, the major products are fac-M(CO)3(η2-P3)X (syn and anti isomers) and cis,fac-M(CO)2(η3-P3)X, and with P3P', the major product for each metal is cis,mer-M(CO)2(η3-P3P')X, but cis-[M(CO)2-(η4-P3P')]X and fac-[Re(CO)3(η3-P3P')]X are also characterized. Addition of MeI to those complexes containing pendant phosphine groups produces the corresponding phosphonium cations without affecting the remainder of the molecule. On the voltammetric time scale, electrochemical oxidation of cis,fac-Mn(CO)2(η3-P3)X yields the corresponding 17e cation cis,fac-[Mn(CO)2(η3-P3)X]+, but on the longer time scale of exhaustive electrolysis or chemical oxidation, the product is fac-[Mn(CO)3(η3-P3)]+. In contrast, the rhenium cation cis,fac-[Re(CO)2(η3-P3)X]+ is stable on the synthetic time scale, but upon oxidation of cis,fac-Re(CO)2(η3-P3)X with NOBF4, the final product is the 18e [Re(CO)(NO)(η3-P3)X]+. cis,mer-Mn(CO)2(η3-P3P')X is reversibly oxidized to cis,mer-[Mn(CO)2(η3-P3P')X]+ on the voltammetric time scale, but on the longer synthetic time scale, the product isomerizes to trans-[Mn(CO)2(η3-P3P')X]+, which can be reduced to trans-Mn(CO)2(η3-P3P')X. Upon voltammetric oxidation, the corresponding rhenium complexes show an initial irreversible response associated with the pendant phosphine group prior to the reversible oxidation of the metal on the synthetic time scale; spectroscopic data indicate formation of cis,mer-Re(CO)2(η3-P3P'O)X. The complex cis,mer-[Re(CO)2(η3-P3P'Me)X]+ shows only the reversible metal oxidation response. ESMS data are obtained directly for the methylated cationic complexes, and neutral complexes are either oxidized or adducted with sodium ions to produce cationic species.
AB - The reactions of M(CO)5X (M = Mn, Re; X = Cl, Br) with {Ph2PCH2}3CCH3 (P3) and {Ph2P(CH2)2}3P (P3P') are investigated, and the products are characterized by IR, NMR (31P and 13C), and electrospray mass spectrometric (ESMS) techniques. With P3, the major products are fac-M(CO)3(η2-P3)X (syn and anti isomers) and cis,fac-M(CO)2(η3-P3)X, and with P3P', the major product for each metal is cis,mer-M(CO)2(η3-P3P')X, but cis-[M(CO)2-(η4-P3P')]X and fac-[Re(CO)3(η3-P3P')]X are also characterized. Addition of MeI to those complexes containing pendant phosphine groups produces the corresponding phosphonium cations without affecting the remainder of the molecule. On the voltammetric time scale, electrochemical oxidation of cis,fac-Mn(CO)2(η3-P3)X yields the corresponding 17e cation cis,fac-[Mn(CO)2(η3-P3)X]+, but on the longer time scale of exhaustive electrolysis or chemical oxidation, the product is fac-[Mn(CO)3(η3-P3)]+. In contrast, the rhenium cation cis,fac-[Re(CO)2(η3-P3)X]+ is stable on the synthetic time scale, but upon oxidation of cis,fac-Re(CO)2(η3-P3)X with NOBF4, the final product is the 18e [Re(CO)(NO)(η3-P3)X]+. cis,mer-Mn(CO)2(η3-P3P')X is reversibly oxidized to cis,mer-[Mn(CO)2(η3-P3P')X]+ on the voltammetric time scale, but on the longer synthetic time scale, the product isomerizes to trans-[Mn(CO)2(η3-P3P')X]+, which can be reduced to trans-Mn(CO)2(η3-P3P')X. Upon voltammetric oxidation, the corresponding rhenium complexes show an initial irreversible response associated with the pendant phosphine group prior to the reversible oxidation of the metal on the synthetic time scale; spectroscopic data indicate formation of cis,mer-Re(CO)2(η3-P3P'O)X. The complex cis,mer-[Re(CO)2(η3-P3P'Me)X]+ shows only the reversible metal oxidation response. ESMS data are obtained directly for the methylated cationic complexes, and neutral complexes are either oxidized or adducted with sodium ions to produce cationic species.
UR - https://www.scopus.com/pages/publications/0034675544
U2 - 10.1021/ic0000294
DO - 10.1021/ic0000294
M3 - Article
C2 - 11196942
SN - 0020-1669
VL - 39
SP - 4696
EP - 4703
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 21
ER -