Ruthenium(II) thiol and H2S complexes: synthesis, characterization, and thermodynamic properties.

The known, green, five-coordinate species trans-RuCl(2)(P-N)(PPh(3)) react with R'SH thiols to give yellow cis-RuCl(2)(P-N)(PPh(3))(R'SH) products (P-N = o-diphenylphosphino-N,N'-dimethylaniline; R' = alkyl). The MeSH and EtSH compounds are structurally characterized, with the former being the first reported for a transition metal-MeSH complex, while the thiol complexes with R' = (n)Pr, (i)Pr, (n)Pn (pentyl), (n)Hx (hexyl), and Bn (benzyl) are synthesized in situ. Other trans-RuX(2)(P-N)(PR(3)) complexes (X = Br, I; R = Ph, p-tolyl) are synthesized, and their H(2)S adducts, of a type reported earlier by our group, are also prepared.

Reactivity of the bridged-sulfide complex Pd2Cl2(μ-S)(μ-dmpm)2 toward electrophiles.

The dipalladium(I) complex Pd(2)Cl(2)(dmpm)(2) (1a) [dmpm = bis(dimethylphosphino)methane] is known to react with elemental sulfur (S(8)) to give the bridged-sulfide complex Pd(2)Cl(2)(μ-S)(dmpm)(2) (2a) but, in the presence of excess S(8), PdCl(2)[P,S-dmpm(S)] (4a) and dmpm(S)(2) are generated. Treatment of 1a with elemental selenium (Se(8)), however, gives only Pd(2)Cl(2)(μ-Se)(dmpm)(2) (3a). Complex 4a is best made by reaction of trans-PdCl(2)(PhCN)(2) with dmpm(S).

Reactions of the bis(dialkylphosphino)methane complexes Pd2X2(μ-R2PCH2PR2)2 (X = halogen, R = Me or Et) with H2S, S8, COS, and CS2; detection of reaction intermediates.

The Pd(2)X(2)(dmpm)(2) complexes [X = Cl (1a), Br (1b), I (1c); dmpm = bis(dimethylphosphino)methane. In all the dipalladium complexes mentioned in this paper, the dmpm, depm, and dppm ligands (unless stated otherwise) are bridging, but for convenience the μ-symbol is omitted.] react with H(2)S to yield H(2) and the bridged-sulfido complexes Pd(2)X(2)(μ-S)(dmpm)(2) (2a-c), of which 2a and 2b are structurally characterized.

Solution behavior and structural diversity of bis(dialkylphosphino)methane complexes of palladium.

The preparation of dipalladium complexes containing sterically nondemanding diphosphine (P-P) ligands of the type R(2)PCH(2)PR(2) where R = Me (dmpm) or Et (depm) is reported. Variable-temperature (1)H NMR spectra of the Pd(I)(2) complexes Pd(2)X(2)(dmpm)(2) (X = Cl, Br, or I; the P-P ligands in the Pd(2) complexes are always bridged, but for convenience, the micro -symbol is omitted) show the complexes to be fluxional in solution, the barriers to a ring-flipping process being DeltaG( double dagger ) = 37.9, 39.

Dlf complexes with uniform coordination geometry: structural and magnetic properties of an LnNi2 core supported by a heptadentate amine phenol ligand.

The synthesis and physical characterization of a series of lanthanide (Ln(III)) and nickel (Ni(II)) mixed trimetallic complexes with the heptadentate (N(4)O(3)) amine phenol ligand H(3)trn [tris(2'-hydroxybenzylaminoethyl)amine] has been accomplished in order to extend our understanding of how amine phenol ligands can be used to coaggregate d- and f-block metal ions and to investigate further the magnetic interaction between these ions. The one-pot reaction in methanol of stoichiometric amounts of H(3)trn with NiX(2).6H(2)O (X = ClO(4), NO(3)) followed by addition of the corresponding LnX(3).

Synthesis, characterization, and solution redox properties of (trimpsi)M(CO)(2)(NO) complexes [M = V, Nb, Ta; trimpsi = (t)BuSi(CH(2)PMe(2))(3)].

Treatment of [Et(4)N][M(CO)(6)] (M = Nb, Ta) with I(2) in DME at -78 degrees C produces solutions of the bimetallic anions [M(2micro-I)(3)(CO)(8)](-). Addition of the tripodal phosphine (t)BuSi(CH(2)PMe(2))(3) (trimpsi) followed by refluxing affords (trimpsi)M(CO)(3)I [M = Nb (1), Ta (2)], which are isolable in good yields as air-stable, orange-red microcrystalline solids. Reduction of these complexes with 2 equiv of Na/Hg, followed by treatment with Diazald in THF, results in the formation of (trimpsi)M(CO)(2)(NO) [M = Nb (3), Ta (4)] in high isolated yields.

Nitride formation by thermolysis of a kinetically stable niobium dinitrogen complex.

The reduction of [P(2)N(2)]NbCl (where [P(2)N(2)] = PhP(CH(2)SiMe(2)NSiMe(2)CH(2))(2)PPh) with KC(8) under a dinitrogen atmosphere generates the paramagnetic dinuclear dinitrogen complex ([P(2)N(2)]Nb)(2)(mu-N(2)) (2). Complex 2 has been characterized crystallographically and by EPR spectroscopy. Variable-temperature magnetic susceptibility measurements indicate that 2 displays antiferromagnetic coupling between two Nb(IV) (d(1)) centers.

Di-mu-methoxy-bis[(eta(5)-cyclopentadienyl)(nitrosyl-kappa N)(trimethylsilylmethyl)molybdenum(II)].

The title complex, [Mo(2)(C(5)H(5))(2)(CH(3)O)(2)(C(4)H(11)Si)(2)(NO)(2)], is formed in high yield by treating [CpMo(NO)(CH(2)SiMe(3))(2)] (Cp is cyclopentadienyl) with methanol. The nitrosyl ligands are nearly linear [O[bond]N[bond]Mo 170.1 (4) and 170.

(Eta5-cyclopentadienyl)(p-fluorophenoxo)(nitrosyl)(trimethylsilylmethyl)molybdenum(II).

The title complex, [Mo(C(5)H(5))(C(6)H(4)FO)(C(4)H(11)Si)(NO)], is formed by reacting CpMo(NO)(CH(2)SiMe(3))(2), where Cp is cyclopentadienyl, with one equivalent of p-FC(6)H(4)OH. The complex exhibits the expected piano-stool molecular structure, with a linear nitrosyl ligand [Mo-N-O 168.2(2) degree] having Mo-N and N-O distances of 1.

Phosphorus phenyl-group activation by reduced zirconium and niobium complexes stabilized by the [P2N2] macrocycle.

Reduction of [P2N2]ZrCl2 (where [P2N2] = PhP(CH2SiMe2NSiMe2CH2)2PPh) with KC8 under argon generates the phosphorus phenyl bridged bimetallic complex where the bridging phenyl groups are formally reduced to bis(allyl) dianions. Similar reduction of [P2N2]NbCl caused the one-electron reduction of the phosphorus phenyl group to generate a cyclohexadienyl moiety via a C-C bond formation between the ipso carbons of the two phenyl groups.

Stoichiometric O(2) Oxidation of Bis(Thioether)(Octaethylporphyrinato)ruthenium(II) Complexes to the Corresponding Sulfoxide Species in Acidic Media. Structural Confirmation of S-Bonded Sulfoxides.

Exposure to O(2) (or air) of a CH(2)Cl(2), benzene, or toluene solution containing PhCO(2)H and Ru(OEP)(RR'S)(2) (where OEP = the dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin, R = methyl, ethyl, or decyl, and R' = methyl or ethyl), at ambient conditions, results in the selective oxidation of the axial ligand(s) on the metalloporphyrin complex to the corresponding sulfoxide(s). For example, a CD(2)Cl(2) solution of Ru(OEP)(dms)(2) (dms = dimethyl sulfide) and PhCO(2)H, exposed to 1 atm of O(2) at approximately 20 degrees C for 35 h, is oxidized to Ru(OEP)(dmso)(2), and the intermediates Ru(OEP)(dms)(dmso), [Ru(OEP)(dms)(2)][PhCO(2)], and Ru(OEP)(dms)(PhCO(2)) are identified (s implies sulfur-bonded). Mechanisms invoking in situ formation of H(2)O(2), disproportionation of Ru(III) species, and Ru(IV)=O intermediates are proposed for the O(2) oxidation of the thioether ligands.

Synthesis and Structure of [{Mo(CO)(4)}(2)(cis-&mgr;-F(2)SbF(4))(3)](x)()[Sb(2)F(11)](x)(): An Ionic Coordination Polymer.

The oxidation of molybdenum hexacarbonyl, Mo(CO)(6), by antimony(V) fluoride, SbF(5), at 60 degrees C in an excess of liquid SbF(5), produces polymeric [{Mo(CO)(4)}(2)(cis-&mgr;-F(2)SbF(4))(3)](x)()[Sb(2)F(11)](x)() as the main product. Recrystallization from HF-SbF(5) produces orange prismatic crystals, suitable for a single-crystal X-ray diffraction study. Crystals of [{Mo(CO)(4)}(2)(cis-&mgr;-F(2)SbF(4))(3)](x)()[Sb(2)F(11)](x)() are monoclinic, space group P2(1)/c (No.

Kinetic and Mechanistic Aspects of Sulfur Recovery from Pd(2)I(2)(&mgr;-S)(&mgr;-dpm)(2) Using I(2) and Structures of Pd(II) Complexes with the Chelated Monosulfide of dpm.

The Pd(2)X(2)(&mgr;-S)(dpm)(2) complexes (2) (X = I, Br) react with halogens to yield PdX(2)(dpm) (3) and elemental sulfur. Kinetic and mechanistic studies on the X = I system in CHCl(3) reveal that the reaction proceeds via addition of I(2) to give Pd(2)I(4)(dpm)(2) (4c), which then undergoes unimolecular decomposition to generate PdI(2)(dpm) (3c); the liberated sulfur concatenates to form elemental S(8). The addition reaction is in the stopped-flow time regime and is first-order in both 2c and I(2), with DeltaH() = 32 +/- 1 kJ mol(-)(1) and DeltaS() = -91 +/- 3 J K(-)(1) mol(-)(1).

Pyramidal Inversion at Phosphorus Facilitated by the Presence of Proximate Lewis Acids. Coordination Chemistry of Group 13 Elements with the Macrocyclic Bis(amidophosphine) Ligand [P(2)N(2)] ([P(2)N(2)] = [PhP(CH(2)SiMe(2)NSiMe(2)CH(2))(2)PPh]).

Investigations on the preparation of four- and five-coordinate aluminum and gallium bis(amidophosphine) derivatives are reported. The reaction of the macrocyclic ligand precursor anti-Li(2)(THF)(2)[P(2)N(2)] ([P(2)N(2)] = [PhP(CH(2)SiMe(2)NSiMe(2)CH(2))(2)PPh]) with AlCl(3) or GaCl(3) in toluene at 25 degrees C leads to the formation of the four-coordinate species anti-MCl[P(2)N(2)] (M = Al (1), Ga (2)). An X-ray diffraction study of anti-GaCl[P(2)N(2)] shows it to be monomeric with a distorted tetrahedral geometry at Ga; only one of the phosphine donors of the [P(2)N(2)] ligand binds to the gallium, resulting in the retention of the anti-configuration.

Synthesis and Structure of a Zirconium Dinitrogen Complex with a Side-On Bridging N(2) Unit.

Reduction of Zr(O-2,6-Me(2)C(6)H(3))Cl(2)[N(SiMe(2)CH(2)PPr(i)(2))(2)] with sodium amalgam under dinitrogen yields the dinuclear zirconium dinitrogen complex {[(Pr(i)(2)PCH(2)SiMe(2))(2)N]Zr(O-2,6-Me(2)C(6)H(3))}(2)(&mgr;-eta(2):eta(2)-N(2)). Solid state structural analysis shows that the dinitrogen unit is bound in a side-on mode of coordination with the N-N bond distance at 1.528(7) Å; resonance Raman spectra show a band at 751 cm(-)(1) for nu(N-N), which is consistent with this very long bond.

Synthesis, Structure, and Reactivity of [RuCl(PP)L]PF(6) (PP = (PPh(3))(2), Ph(2)P(CH(2))(4)PPh(2); L = P(py)(3), PPh(py)(2), py = 2-pyridyl). The "Missing" P,N,N'-Coordination Mode for 2-Pyridylphosphines.

The complexes [RuCl(PPh(3))(2)(P,N,N'-PPh(3-)(x)()(py)(x)())]PF(6) (x = 2, 1b; 3, 1c; py = 2-pyridyl) were isolated from the reaction of RuCl(2)(PPh(3))(3) with 1 equiv of PPh(3-)(x)()(py)(x)() and NH(4)PF(6) in acetone. Crystals of 1b (C(52)H(43)ClF(6)N(2)P(4)Ru) are monoclinic, a = 17.795(2), b = 11.

Synthesis and Structure of a New Lithium Amide Ligand Precursor: A Tridentate Nitrogen-Based Donor Set of the Formula N(SiMe(2)CH(2)NMe(2))(2). Synthesis and Structure of the Group 4 Amides MCl(3)[N(SiMe(2)CH(2)NMe(2))(2)] (M = Ti, Zr, Hf).

The new lithium amide LiN(SiMe(2)CH(2)NMe(2))(2) was prepared by reaction of NH(3) with the corresponding silylamine Me(2)NSiMe(2)CH(2)NMe(2) followed by addition of butyllithium. This lithium derivative exists as a dimer in the solid state wherein the two lithium ions are bridged by the two amido units with the amine arms of each unit bonded to opposite lithium centers in an overall pseudo D(2) structure; however, in solution, a fluxional process serves to interconvert the enantiomeric forms of the dimer unit. The coordination chemistry of the lithium amide dimer has been investigated; reaction with a series of group 4 starting halides, MCl(4), leads to the corresponding complexes MCl(3)[N(SiMe(2)CH(2)NMe(2))(2)], where M = Ti, Zr, and Hf.

Effect of Pyridyl Donors in the Chelation of Aluminum(III), Gallium(III), and Indium(III).

A new preparation of N,N'-bis(2-pyridylmethyl)ethylenediamine-N,N'-diacetic acid (H(2)bped) is reported, and its properties of complexation with Al(III), Ga(III), In(III), and Co(III) are investigated. The molecular structure of the cobalt(III) complex [Co(bped)]PF(6).CH(3)CN.

Characterization of Five-Coordinate Ruthenium(II) Phosphine Complexes by X-ray Diffraction and Solid-State (31)P CP/MAS NMR Studies and Their Reactivity with Sulfoxides and Thioethers.

31P CP/MAS NMR spectroscopy is examined as a method of characterization for ruthenium(II) phosphine complexes in the solid state, and the results are compared with X-ray crystallographic data determined for RuCl(2)(dppb)(PPh(3)) (dppb = Ph(2)P(CH(2))(4)PPh(2)), RuBr(2)(PPh(3))(3), and the previously determined RuCl(2)(PPh(3))(3). Crystals of RuBr(2)(PPh(3))(3) (C(54)H(45)Br(2)P(3)Ru) are monoclinic, space group P2(1)/a, with a = 12.482(4) Å, b = 20.

Oxidation Kinetics of the Potent Insulin Mimetic Agent Bis(maltolato)oxovanadium(IV) (BMOV) in Water and in Methanol.

The kinetics of oxidation of bis(maltolato)oxovanadium(IV), BMOV or VO(ma)(2), by dioxygen have been studied by UV-vis spectroscopy in both MeOH and H(2)O media. The VO(ma)(2):O(2) stoichiometry was 4:1. In aqueous solution, the pH-dependent rate of the VO(ma)(2)/O(2) reaction to generate cis-[VO(2)(ma)(2)](-) is attributed to the deprotonation of coordinated H(2)O, the deprotonated species [VO(ma)(2)(OH)](-) being more easily oxidized (k(OH) = 0.

Bis(ligand) Rhenium(V) and Technetium(V) Complexes of Two Naturally Occurring Binding Moieties (Oxazoline and Thiazoline).

Attempts to prepare tris(ligand) metal complexes of technetium in intermediate oxidation states with potentially bidentate oxazoline- and thiazoline-containing ligands were unsuccessful; when pertechnetate was reduced in the presence of excess ligand, TcO(2).xH(2)O was produced. Instead, by reaction with preformed M.