Treatment of [Ir(H)(PCy
3)
2Cl
2] with K[N(Pr
i2PS)
2] yielded the iridium(III) hydride complex cis-[Ir(H)(PCy
3){N(Pr
i2PS)
2}
2], which could be protonated by HBF
4 to give a dicationic cis-[Ir(H)(PCy
3){HN(Pr
i2PS)
2}
2][BF
4]
2. Reaction of [Ir(COE)
2{N(Pr
i2PS)
2}] with PPh
3 gave a iridium bis-triphenylphosphine complex [Ir(PPh
3)
2{N(Pr
i2PS)
2}].
A series of rhodium triphenylphosphine complexes with [N(R
2PQ)
2]
- ligands, [Rh(PPh
3)
2{N(R
2PQ)
2}], have been synthesized from reaction of [Rh(PPh
3)
3Cl] with K[N(R
2PQ)
2] (R = Pr
i, Bu
t; Q = O, S and Se). [Rh(PPh
3)
2{N(Pr
i2PQ)
2}(η
2-O
2)] (Q = S, Se) were isolated when [Rh(PPh
3)
2{N(Pr
i2PQ)
2}] were recrystallized for a long time with leakage of air. [Rh(PPh
3)
2{N(Pr
i2PS)
2}] can catalyze the hydrosilylation of acetophenone with H
2SiPh
2. [Rh(PPh
3)
2{N(Pr
i2PS)
2}] underwent reversible oxidative addition with triethylsilane and benzoyl chloride to give [Rh(H)(PPh
3){N(Pr
i2PS)
2}(SiEt
3)] and [Rh(COPh)(PPh
3)
2{N(Pr
i2PS)
2}(Cl)], respectively. Reaction of [Rh(PPh
3)
2{N(Pr
i2PS)
2}] with HCl gave a mixture of [Rh(PPh
3){N(Pr
i2PS)
2}
2Cl] and a Rh-hydride species. Oxidative addition of [Rh(PPh
3)
2{N(Pr
i2PQ)
2}] (Q = S, Se) with MeI afforded five-coordinated Rh(III) complexes [Rh(PPh
3){N(Pr
i2PQ)
2}(CH
3)I]. Treatment of [Rh(PPh
3){N(Pr
i2PS)
2}(CH
3)I] with K[N(Pr
i2PS)
2] resulted in the formation of the bis-chelated Rh-methyl complex [Rh(CH
3){N(Pr
i2PS)
2}
2], which could be protonated by triflic acid to give dicationic [Rh(CH
3){HN(Pr
i2PS)
2}
2][OTf]
2.
Reaction of [Ru(=CHPh){N(Pr
i2PS)
2}(PCy
3)Cl] with excess NaOMe led to the formation of the ruthenium hydride complex [Ru(H){N(Pr
i2PS)
2}{PCy
2(η
2-C
6H
9)}] containing a κ
3-dicyclohexyl(η
2-cyclohex-3-enyl) phosphine ligand. The formation of the hydride complex involved a Ru-hydride benzylidene intermediate derived from β-hydrogen elimination of a Ru-OMe precursor, followed by double intramolecular C-H activation of a cyclohexyl group in PCy
3.
Treatment of [Et
4N]
2[WSe
4] with dimethyl and diethyl acetylenedicarboxylate afforded the [2+3] cycloaddition adducts [Et
4N]
2[W(η
2-C
2(CO
2R)
2){Se
2C
2(CO
2R)
2}
2] (R = Me, Et). These W
IV bis(diselenolene) complexes have a distorted trigonal prismatic geometry containing a η
2-alkyne ligand that act as 4-electron donor ligand. In addition, a small amount of [Et
4N]
2[W(Se){Se
2C
2(CO
2Me)
2}
2], which may be formed by reaction of [Et
4N]
2[W(η
2-C
2(CO
2Me)
2){Se
2C
2(CO
2Me)
2}
2] with the Se derived from the decomposed [WSe
4]
2-, was isolated.
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