Reduction of [Cp*Ru{N(Ph
2PS)
2}Cl] with Li[BEt
3H] yielded 16-electron [Cp*Ru{N(Ph
2PS)
2}], which reacted with 2-electron ligands to give 18-electron adducts. Oxidation of [Cp*Ru{N(Ph
2PS)
2}] with tetramethylthiuram disulfide afforded [Cp*Ru(S
2CNMe
2)
2][N(Ph
2PS)
2]. Reaction of [(η
6-C
6Me
6)RuCl
2]
2 with AgOTf (OTf
- = triflate) followed by K[N(R
2PS)
2] gave 16-electron [(η
6-C
6Me
6)Ru{N(R
2PS)
2}][OTf], which reacted with 2-electron ligands to give 18-electron adducts. Treatment of [(η
6-C
6Me
6)Ru{N(Pr
i2PS)
2}][OTf] with NaBH
4 and Li[BEt
3H] afforded Ru(II) hydride and ethyl compounds, respectively.
[Ru(=CHPh){N(Pr
i2PS)
2}(PCy
3)Cl] synthesized from [Ru(=CHPh)(PCy
3)
2Cl
2] with K[N(Pr
i2PS)
2] underwent chloride substitution with NaN
3 and Tl[OPh]. [Ru(=CHPh){N(Pr
i2PS)
2}(PCy
3)Cl] can catalyze ring-opening polymerization of cycloolefins and ring-closing metathesis of diethyl diallylmalonate. Treatment of [Ru{N(Pr
i2PS)
2}
2(PPh
3)] with HBF
4 and MeOTf led to N-protonation and S-methylation of the coordinated [N(Pr
i2PS)
2]
- ligands, respectively. [Ru{N(R
2PS)
2}
2(PPh
3)] can catalyze hydrogenation of styrene via a Ru-η
2-H
2 intermediate that has been characterized by
1H NMR spectroscopy.
Reduction of trans-[Os{N(Pr
i2PS)
2}
2(O)
2] with N
2H
4•H
2O afforded a dinitrogen complex [Os{N(Pr
i2PS)
2}
2(N
2)(solv)], which reacted with RCN, R’NC and SO
2 to give trans-[Os{N(Pr
i2PS)
2}
2(RCN)
2], trans-[Os{N(Pr
i2PS)
2}
2(R’NC)
2] and [Os{N(Pr
i2PS)
2}
2(SO
2)(H
2O)], respectively. Reduction of trans-[Os{N(Pr
i2PS)
2}
2(O)
2] with PMePh
2, phenylhydrazine and SnCl
2 afforded cis-[Os{N(Pr
i2PS)
2}
2(PMePh
2)
2], trans-[Os{N(Pr
i2PS)
2}
2(N
2Ph)
2] and trans-[Os{N(Pr
i2PS)
2}
2Cl
2], respectively. Air oxidation of [Os{N(Pr
i2PS)
2}
2(N
2)(solv)] in hexane/MeOH gave trans-[Os{N(Pr
i2PS)
2}
2(OMe)
2]. trans-[Os{N(Pr
i2PS)
2}
2(O)
2] and trans-[Os{N(Pr
i2PS)
2}
2(OMe)
2] are capable of catalyzing aerobic oxidation of PPh
3, possibly via an Os(IV) intermediate.
A series of iridium and rhodium olefin complexes with [N(R
2PQ)
2]
- (R = Pr
i, Q = S; R = Ph, Q = O) have been synthesized. Oxidative addition of [M(ol)
2{N(Ph
2PO)
2}] yielded [M(ol)
2{N(Ph
2PO)
2}(CH
3)(OTf)] (M = Ir, Rh; (ol)
2 = COD, (COE)
2, where COD = cyclooctadiene, COE = cyclooctene). Reaction of [Rh(COE)
2Cl]
2 with K[N(Pr
i2PS)
2] afforded a tetra-nuclear sulfido cluster [Rh
4(μ3-S)
2{Pr
i2PNP(S)Pr
i2}
2{N(Pr
i2PS)
2}
2], which underwent reversible oxidative addition with MeI. [Rh
4(μ
3-S)
2{Pr
i2PNP(S)Pr
i2}
2{N(Pr
i2PS)
2}
2] is capable of catalyzing hydrosilylation of acetophenone and hydrogenation of styrene.
Reaction of [Ru(PPh
3)
3Cl
2] with K[N(Ph
2PO)
2] afforded [Ru{N(Ph
2PO)
2}(PPh
3)
2Cl], which reacted with 4-t-butylbenzonitrile and SO
2 to give the corresponding adducts. Treatment of [Ru(CO)
2Cl
2]
n with K[N(Ph
2PO)
2] afforded a K/Ru bimetallic compound [K{N(Ph
2PO)
2}Ru{N(Ph
2PO)
2}(CO)
2Cl]
2 that was converted to [Ru{N(Ph
2PO)
2}
3] after irradiation with UV light. Treatment of [Ru(=CHPh)(PCy
3)
2Cl
2] with [Ag{N(Ph
2PO)
2}]
4 yielded cis-[Ru(=CHPh)(PCy
3){N(Ph
2PO)
2}
2], which can catalyze alcohol oxidation and olefin epoxidation with PhIO, presumably via a Ru-oxo intermediate.
Photolysis of cis-[Ru(NO)Cl{N(Ph
2PO)
2}
2] in CH
2Cl
2/solv afforded the corresponding ruthenium(III) solveno complexes cis-[Ru(solv)Cl{N(Ph
2PO)
2}
2] (solv = MeCN, H
2O). Similarly, photolysis [Ru(NO)(L
OEt)Cl
2] (L
OEt- = [CpCo{P(O)(OEt)
2}
3]
-) yielded [Ru(solv)(L
OEt)Cl
2]. Reaction of [Ru(dtbpy)(NO)Cl
3] (dtbpy = 4,4’-di-tert-butyl-2,2’-bipyridyl) with Na[SAr] afforded mer-[Ru(dtbpy)(NO)(SAr)
3] (Ar = 2,6-Me
2C
6H
3, C
6F
4H). mer-[Ru(dtbpy)(NO)(SC
6F
4H)
3] that underwent photorelease of NO with visible light. Five-coordinated [Rh(NO){N(R
2PQ)
2}
2] were synthesized by reaction of [Rh(NO)(PPh
3)
2Cl
2] with K[N(R
2PQ)
2] (R = Ph, Pr
i; Q = S, Se). The nitrosyl ligands in [Rh(NO){N(R
2PQ)
2}
2] are bent, whereas those in the ruthenium analogues [Ru(NO)Cl{N(R
2PQ)
2}
2] are linear.
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