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The solid-state structures of compounds PPh2CH2SPh (1) and PPh2C6H4SMe (2) were determined by single crystal X-ray diffraction. Experimental results on the molecular structures of compounds 1 and 2 were supported by Hirshfeld surface analysis and Density Functional Theory (DFT). The computed values calculated at DFT level using B3LYP function with 6-311++G (3df, 3pd) (P, S) and 6-31G* (C, H) basis sets are in good agreement with the experimental results. [ABSTRACT FROM AUTHOR]

A series of new heteromultinuclear FeI/RuII clusters are described. The complexes (η6‐arene)RuFe2S2(CO)6 (arene = p‐cymene 1, C6Me62) and Fe2[μ‐S (Cp*Ru)(CO)2]2(CO)6 (Cp* = η5‐C5Me5) (3) were prepared by the reduction reactions of (μ‐S)2Fe2(CO)6 with 2 equiv of LiHBEt3, followed by treatment (μ‐SLi)2Fe2(CO)6 with ruthenium‐arene complexes Ru2(μ‐Cl)2Cl2(η6‐arene)2 or Cp*Ru (CO)2Cl in 22–33% yields. Further reactions of 1 and 2 with 1 equiv of triphenylphosphine in the presence of the decarbonylating agent Me3NO·2H2O, afforded the corresponding monophosphine‐substituted FeI/RuII complexes (η6‐arene)RuFe2S2(CO)5(Ph3P) (arene = p‐cymene 4, C6Me65) in 75% and 78% yields. While treatment of parent complex 1 or 2 with 1 equiv of diphosphine Ph2PCH2PPh2 (dppm) in xylene at reflux temperature resulted in the formation of the diphosphine‐bridged RuFe2S2(CO)9 derivate RuFe2S2(CO)7(dppm) (6). The possible pathway for the formation was proposed. Two isomers of novel macrocyclic complexes involve the (η6‐arene) Ru‐bridged quadruple‐butterfly Fe/S clusters [{μ‐S (CH2)3S‐μ}{(μ‐CS2)Fe2(CO)6}2]2[(η6‐arene)Ru]2 (arene = p‐cymene 7a and 7b, C6Me68a and 8b) were isolated by reactions of two μ‐CS2‐containing dianion [{μ‐S (CH2)3S‐μ}{(μ‐S=CS)Fe2(CO)6}2]2− with [Ru2(μ‐Cl)2Cl2(η6‐arene)2], in which the propylene groups are attached to two S atoms by ee and ea types of bonds respectively. All the new complexes 1–8 have been characterized by elemental analysis, spectroscopy, and particularly for 1–6, 7b and8a by X‐ray crystallography. In addition, the electrochemical properties of representative complexes 1–4 and 6 have been investigated. [ABSTRACT FROM AUTHOR]

In this paper, five diiron propane-1,3-dithiolate complexes containing substituted phosphine ligands were prepared and structurally characterized. Treatment of [Fe2(CO)6(μ-SCH2CH2CH2S)] (1) with a monophosphine ligand methyl diphenylphosphinite, ethyl diphenylphosphinite, 4-(dimethylamino)phenyldiphenylphosphine, tris(2-methoxyphenyl)phosphine, or tris(4-chlorophenyl)phosphine in the presence of Me3NO·2H2O as the decarbonylating agent gave the corresponding phosphine-substituted analogues [Fe2(CO)5(L)(μ-SCH2CH2CH2S)] [L = Ph2POCH3, 2; Ph2POCH2CH3, 3; Ph2P(4-C6H4 NMe2), 4; P(2-C6H4OCH3)3, 5; P(4-C6H4Cl)3, 6] in 73–93% yields. Complexes 2–6 have been characterized by elemental analysis, spectroscopy, and X-ray crystallography. Additionally, electrochemical studies have shown that 2–6 can catalyze the reduction of protons to H2 in the presence of HOAc. [ABSTRACT FROM AUTHOR]

The reactions of the starting complex, [Fe2(CO)6{μ-SCH2CH (CH2CH3)S}] (1), with the phosphine ligands tris(4-methylphenyl)phosphine, diphenyl-2-pyridylphosphine, tris(4-fluorophenyl)phosphine, 2-(diphenylphosphino)benzaldehyde, or benzyldiphenylphosphine in the presence of the decarbonylating agent Me3NO·2H2O yielded the corresponding phosphine-substituted diiron butane-1,2-dithiolate complexes [Fe2(CO)5(L){μ-SCH2CH(CH2CH3)S}] (L = P(4-C6H4CH3)3, 2; Ph2P(2-C5H4N), 3; P(4-C6H4F)3, 4; Ph2P(2-C6H4CHO), 5; Ph2PCH2Ph, 6) in 75%–87% yields. The complexes have been characterized by elemental analysis, IR, 1H, and 31P{1H} NMR spectroscopy, as well as by single-crystal X-ray diffraction analysis. Moreover, the electrochemistry of 2–4 was studied by cyclic voltammetry, suggesting that they can catalyze the reduction of protons to H2 in the presence of HOAc. [ABSTRACT FROM AUTHOR]

The synthesis and solid state structures of homo- and heteroleptic Zr and Ti complexes of 2-(diphenylphosphino)pyrrolide (NP) are reported. The homoleptic Zr(NP) 4 ( 1 ) and Ti(NP) 4 ( 2 ) are 8-coordinate in the solid state, and both show extremely long M–P bonds of approximately 2.9 Å. In solution, the phosphine ligands in all complexes are labile: in the titanium complexes phosphine dissociation is rapid at room temperature and equilibrates all phosphines into a single 31 P resonance, whereas in the Zr complex 1 dissociation is slower and full equilibration does not occur until 90 °C. The potential to utilize these novel complexes as metalloligands toward other transition metals is discussed. [ABSTRACT FROM AUTHOR]

Reaction of (?3-S)FeCo2(CO)9(A) with PPh3at room temperature in CH2Cl2gave?3-sulfido dicobalt-iron clusters (?3-S)FeCo2(CO)8(PPh3) (1) and (?3-S)FeCo2(CO)7(PPh3)2(2) in 37 and 54% yields, whereas reaction ofAwith 1,4-bis(diphenylphosphino)butane (Ph2PCH2CH2CH2CH2PPh2, dppb) afforded [(?3-S)FeCo2(CO)8]2(Ph2PCH2CH2CH2CH2PPh2) (3) in 49% yield. Complexes1–3were characterized by elemental analysis, spectroscopy, and for1and3by X-ray crystallography. [ABSTRACT FROM AUTHOR]

Abstract: Cyclometalated platinum(II) complex [Pt(C^N)Cl(dmso)], 1, in which C^N = N(1),C(2′)-chelated deprotonated 2-phenylpyridine and dmso = dimethylsulfoxide, was reacted with 1 equiv of 1,1′-bis(diphenylphosphino)ferrocene, dppf, to give the cyclometalated diplatinum(II) complex [Pt2(C^N)2Cl2(μ-dppf)], 2, along with 0.5 equiv of unreacted dppf. However, the related reaction with 0.5 equiv of dppf produced complex 2 in pure form. Complex 2 in solution was fully characterized by using multinuclear NMR spectroscopy (1H, 13C, 31P, and 195Pt) and a number of 2D NMR experiments. The structure of complex 2 in solid state was determined by X-ray crystallography showing that the bridging dppf ligand is arranged close to “antiperiplanar staggered” conformation. Cytotoxicity of the complex 2 was studied in three human cancer cell lines derived from ovarian carcinoma(CH1), lung carcinoma(A549), and colon carcinoma (SW480) by means of the MTT assay (MTT = 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide). [Copyright &y& Elsevier]

A series of new Fe/Te clusters are described. The phosphine substituted diiron bis(monotellurolate) carbonyls 3–8 can be prepared by CO substitution reactions of the parent compounds 1 and 2 with the corresponding phosphine ligands. 1 and 2 together with the Ph 3 P-substituted models 3 and 4 can be separated into syn - and anti -isomers. While for Me 3 P-substituted and dppm-bridged compounds 5–8 , only anti -forms are found. • A series of structural and functional models of diiron bis(monotellurolate) carbonyls were prepared. • Both anti- and syn -isomers for 1 – 4 were isolated as solid states using the TLC method. • The compounds were fully characterized and for some by X-ray crystallography. • Electrochemical and electrocatalytic properties of 1–8 were investigated. To explore the study of mimicking behaviors of H-cluster by Fe/Te compounds, a series of structural and functional models of diiron bis(monotellurolate) carbonyls have been prepared. Thus, treatment of diaryl ditelluride (ArTe) 2 with Fe 3 (CO) 12 at reflux temperature give parent compounds Fe 2 (μ-TeAr) 2 (CO) 6 (Ar = C 6 H 5 1 , C 6 H 4 -4-F, 2). Further reactions of 1 and 2 with 1 equiv of monophosphines afford the corresponding monophosphine-substituted compounds Fe 2 (μ-TeAr) 2 (CO) 5 L (Ar = C 6 H 5 , L = PPh 3 , 3 ; Ar = C 6 H 4 -4-F, L = PPh 3 ; 4 , Ar = C 6 H 5 , L = PMe 3 , 5 ; Ar = C 6 H 4 -4-F, L = PMe 3 , 6) in 38–60% yields. Of particular interest here, both anti- and syn -isomers for 1–4 are isolated as solid states using the TLC method. While only anti- forms are found in 5 and 6 , the PMe 3 ligand lies on the apical position in 5 , but prefers the basal position in 6. The diphosphine-bridged compounds Fe 2 (μ-TeAr) 2 (CO) 4 (dppm) (Ar = C 6 H 5 , 7 ; Ar = C 6 H 4 -4-F, 8) can be prepared by treatment of 1 and 2 with 1 equiv of bis(diphenylphosphino)methane (dppm) in refluxing xylene in 58% and 64% yields. All the compounds are characterized by elemental analysis, FT-IR, NMR spectroscopy, and particularly for 1- anti / syn , 2- anti / syn , 3- anti / syn , 4- anti and 5 – 8 by X-ray diffraction analyses. In addition, the electrochemical and electrocatalytic properties of 1 – 8 are studied by cyclic voltammetry (CV) in MeCN, indicating that they are all found to be catalysts for H 2 production in the presence of acetic acid (HOAc) under electrochemical conditions. [ABSTRACT FROM AUTHOR]

The synthesis of the metalloligand Ta(κ2-NP) 3 Cl 2 (NP = 2-diphenylphosphinopyrrolide) and its coordination chemistry with group 9 and 10 metals is reported. Treatment of Ta(κ2-NP) 3 Cl 2 with group 9 and 10 metals resulted in clean formation of the heterobimetallic complexes Cl 2 Ta(μ 2 -NP) 3 M (M = Ni (2), Pd (3)) or Cl 2 Ta(μ 2 -NP) 3 MCl (M = Rh (4), Ir (5)). The synthesis of the metalloligand Ta(κ2-NP) 3 Cl 2 (NP = 2-diphenylphosphinopyrrolide) and its coordination chemistry with group 9 and 10 metals is reported. Treatment of Ta(κ2-NP) 3 Cl 2 with group 9 and 10 metals resulted in clean formation of the heterobimetallic complexes Cl 2 Ta(μ 2 -NP) 3 M (M = Ni (2), Pd (3)) or Cl 2 Ta(μ 2 -NP) 3 MCl (M = Rh (4), Ir (5)). Each pair of complexes is isostructural and contains three phosphinopyrrolide ligands that bridge the metal centers. The d10 or d8 complexes are all diamagnetic and X-ray crystallographic analysis reveals similarly short metal - metal distances, ranging from 2.2979(5) Å to 2.4366(2) Å. Despite the similar bonding metrics in 2 – 5, treatment with an L type donor (2,6-dimethylphenylisocyanide (CNXylyl)) reveals 3 different coordination geometries in TaNi(CNXylyl) (6), TaPd(CNXylyl) (7), and TaIr(CNXylyl) (8). While complexes 6, 7, and 8 all bind the isocyanide at the late metal, ligand rearrangements are observed in the first row complex 6. Complex 7 binds the isocyanide in the axial position while equatorial binding is observed in 8. All isocyanide adducts maintain close metal - metal contacts in the solid state. [ABSTRACT FROM AUTHOR]

The reaction of isolable dithiirane 1-oxides with (Ph 3 P) 2 Pt(η 2 -C 2 H 4 ) provided the title complexes in high yields. 31 P NMR spectroscopy of the phosphine ligands of the complexes and x-ray crystallographic analysis of a complex were reported. [ABSTRACT FROM AUTHOR]