The reactivity and stability of P(III)-N and P(III)≈N bonds will be different towards various solvents, bases, and acids because of their difference in bond strength due to different N-pπ-P-dπ donor bonding. For this, a P≈N containing Pd(II) complex, [Pd(DPAP)2] (C1), was synthesized from the reaction between PdCl2(COD) (COD = 1,4-cyclooctadiene) and 2 equiv. DPAP (diphenyl phosphino amino pyri...

The conversion of glycerol into high value products, such as hydrogen gas and 1,3-propanediol (PD), was examined using anaerobic fermentation with heat-treated mixed cultures. Glycerol fermentation produced 0.28 mol-H(2)/mol-glycerol (72 mL-H(2)/g-COD) and 0.69 mol-PD/mol-glycerol. Glucose fermentation using the same mixed cultures produced more hydrogen gas (1.06 mol-H(2)/mol-glucose) but no P...

A new pyrrole based NNN-pincer ligand, 2,5-bis(3,5-dimethylpyrazolylmethyl)pyrrole 2, was readily synthesized in two steps from pyrrole in 56% yield. The lithiation of the pincer ligand 2 using n-BuLi led to isolation of the dimeric lithium complex, [Li{μ-C(4)H(2)N-2,5-(CH(2)Me(2)pz)(2)-N,N,N}](2) 4, in 23% crystalline yield. The transmetalation reaction of 4 with [Pd(PhCN)(2)Cl(2)] afforded th...

A chelating diphosphine ligand with a central N-heterocyclic phosphenium cation (NHP(+)) has been used to explore the coordination chemistry of NHPs with nickel. Treatment of the chlorophosphine precursor [PPP]Cl (1) with stoichiometric Ni(COD)2 affords (PPP)NiCl (8), which is best described as a Ni(II)/NHP(-) phosphido complex formed via oxidative addition of the P-Cl bond. In contrast, treati...

The reactions of [CpMoH(κ(3)-P4)] (2; P4 = meso-o-C6H4(PPhCH2CH2PPh2)2) with protic acids gave [CpMo(κ(4)-P4)](+) (4(+)) via the intermediary formation of [CpMoH2(κ(3)-P4)](+). Treatment of 2 with iodine provided the cationic complex [CpMoHI(κ(3)-P4)][I] (5[I]). Early-late heterobimetallic complexes of the type [CpMoH(μ-P4-1κ(3):2κ)MLnCl] (MLn = Ru(Hmb)Cl (6), Ir(η(5)-C5Me5)Cl (7), Rh(cod), Ir(...

The redox-active metallaphosphine [Fe(dppe)(η(5)-C5Me5)(C≡C-PPh2)] reacts with [Pd(1,5-cod)Cl2] to give mono- and bis-phosphine coordinated palladium centres as a function of stoichiometry, and these complexes provide a stable redox-active platform which allows reversible one-electron {Fe(II)→Fe(III)(+)} oxidations within the palladium coordination sphere.

Abstract New thiosemicarbazone (TSC) ligands, AMT-C N-TSCH (L1), N-TSC(CH3) (L2), CIN-C (L3) and (L4) (AMT = 2-acetyl-5-methylthiophene, TSCH = thiosemicarbazide, TSC(CH3) = 4-methyl-3-thiosemicarbazide, CIN = cinnamaldehyde) were synthesized by condensation reaction. The reaction of [PdCODCl2] with the ligands L1, L2 L4in ratio 1:1 yielded complexes [Pd(L1)Cl] (C1), [Pd(L2)Cl2] (C2), [Pd(L4)2C...

The one-step synthesis (33 % isolated yield) of a novel bicyclic diphosphane, [P(CH2)2NC6H4(4-NMe2)]2, P−P(NMe2), from the reaction [P(CH2OH)4]Cl and H2NC6H4(4-NMe2) in methanol is described. Surprisingly, P−P(NMe2) displays excellent air/solution stability (towards H2O, CH3OH) can also function efficiently as bridging ligand. Hence with [Pd(μ−Cl)(η3-allyl)]2 (η3-allyl=C3H5, C4H7) or [Pd(μ−Cl)(...

Triethylammonium salts of phosphinoferrocene amidosulfonates with electron-rich dialkyphosphino substituents, R2PfcCONHCH2SO3(HNEt3) (4a–c), where fc = ferrocene-1,1′-diyl, and R = i-Pr (a), cyclohexyl (Cy; b), and t-butyl (c), were synthesized from the corresponding phosphinocarboxylic acids-borane adducts, R2PfcCO2H·BH3 (1a–c), via esters R2PfcCO2C6F5·BH3 (2a–c) and adducts R2PfcCONHCH2SO3(HN...

Treatment of [PtI2(COD)] (COD = 1,5-cyclooctadiene) with 2-LiC6H4P(S)Ph2 gives the complex cis-[Pt{κ(2)-2-C6H4P(S)Ph2}2] () containing a pair of ortho-metallated triphenylphosphine sulfide rings. The selenium counterpart, [Pt{κ(2)-2-C6H4P(Se)Ph2}2] (), which exists as cis- and trans-isomers in solution, and the palladium analogues, cis-[Pd{κ(2)-2-C6H4P(X)Ph2}2] [X = S (), Se ()], are obtained b...