Alkylimido osmium(VI) and ruthenium(VI) porphyrins. Crystal and molecular structures of Os(TTP)(O)(NBu~t)·EtOH and Os(4-Cl-TPP)(NBu~t)_2

Oxo(tert-butylimido) or bis(tert-butylimido)osmium(VI) porphyrins Os(Por)(O)(NBut) and Os(Por)(NBut)2, [Por=meso-tetrakis(p-tolyl)porphyrinato (TTP) and meso-tetrakis(4-chlorophe-nyl)porphyrinato (4-Cl-TPP)] were synthesized by air oxidation of bis(tert-butylamme)osmium(II) porphyrins [Os(Por)(H2NBut)2 (Por=TPP, 4-Cl-TPP], depending on whether tert-butylamine is present. The bis(tert-butylamine)ruthenium(II) porphyrins [Ru(Por)(H2NBut)2, Por=TTP, 4-Cl-TPP] can undergo bromine oxidation to give oxo(tert-butylimido)ruthenium(VI) complexes in quantitative yields. All these new complexes were characterized by 1H NMR, UV-Visible and IR spectroscopy. The X-ray crystal structures of Os(TTP)(O)(NBut).EtOH and Os(4-Cl-TPP)(NBut)2 have been determined. Crystal data: for Os(TTP)(O)(NBut).EtOH: monoclinic, space group P21/c, a=1.3546(6) nm, b=2.3180(3) nm, c=1.6817(3) nm, B=90.84(2), V=527.97(1) nm3, Z=4. The Os=O and Os=NBut distances in Os(TTP)(O)(NBut).EtOH are 0.1772(7) nm and 0.1759(9) nm, respectively. The av     

Reactivity of dioxoosmium(VI) porphyrins toward arylhydrazine. Isolation of hydrazidoosmium and amidoosmium porphyrins

Reactions of dioxoosmium(VI) porphyrins [Os(VI)(Por)O(2)] with excess 1,1-diphenylhydrazine in tetrahydrofuran at ca. 55 degrees C for 15 min afforded bis(hydrazido(1-))osmium(IV) porphyrins [Os(IV)(Por)(NHNPh(2))(2)] (1a, Por = TPP (meso-tetraphenylporphyrinato dianion); 1b, Por = TTP (meso-tetrakis(p-tolyl)porphyrinato dianion)), hydroxo(amido)osmium(IV) porphyrins [Os(IV)(Por)(NPh(2))(OH)] (2a, Por = TPP; 2b, Por = TTP), and bis(hydrazido(2-))osmium(VI) porphyrin [Os(VI)(Por)(NNPh(2))(2)] (3c, Por = TMP (meso-tetramesitylporphyrinato dianion)). The same reaction under harsher conditions (in refluxing tetrahydrofuran for ca. 1 h) gave a nitridoosmium(VI) porphyrin, [Os(VI)(Por)(N)(OH)] (4b, Por = TTP). Oxidation of 1a,b with bromine in dichloromethane afforded bis(hydrazido(2-)) complexes [Os(VI)(TPP)(NNPh(2))(2)] (3a) and [Os(VI)(TTP)(NNPh(2))(2)] (3b), respectively. All the new osmium porphyrins were identified by (1)H NMR, IR, and UV-vis spectroscopy and mass spectrometry; the structure of 2b was determined by X-ray crystallography (Os-NPh(2) = 1.944(6) A, Os-OH = 1.952(5) A).     

Reactivity of dioxoruthenium(VI) porphyrins toward amines. Synthesis and characterization of bis(arylamine)ruthenium(II), bis(arylamido)- and bis(diphenylamido)ruthenium(IV), and oxo(tert-butylimido)ruthenium(VI) porphyrins

Reactions of dioxoruthenium(VI) porphyrins, [Ru(VI)O2(Por)], with p-chloroaniline, trimethylamine, tert-butylamine, p-nitroaniline, and diphenylamine afforded bis(amine)ruthenium(II) porphyrins, [Ru(II)(Por)(L)2] (L-p-ClC6H4NH2, Me3N, Por=TTP, 4-Cl-TPP; L=tBuNH2, Por = TPP, 3,4,5-MeO-TPP, TTP, 4-Cl-TPP, 3,5-Cl-TPP) and bis(amido)ruthenium(IV) porphyrins, [Ru(IV)(Por)(X)2] (X=p-NO2C6H4NH, Por=TTP, 4-Cl-TPP; X = Ph2N, Por = 3,4,5-MeO-TPP, 3,5-Cl-TPP), respectively. Oxidative deprotonation of [Ru(II)(Por)(NH2-p-C6H4Cl)2] in chloroform by air generated bis(arylamido)ruthenium(IV) porphyrins, [RuIV(Por)(NH-p-C6H4Cl)2] (Por=TTP. 4-Cl-TPP). Oxidation of [RuII(Por)-(NH2tBu)2] by bromine in dichloromethane in the presence of tert-butylamine and traces of water produced oxo(imido)ruthenium(VI) porphyrins, [RuVI-O(Por)(NtBu)] (Por=TPP, 3,4,5-MeO-TPP, TTP, 4-Cl-TPP, 3,5-Cl-TPP). These new classes of ruthenium complexes were characterized by 1H NMR, IR, and UV/visible spectroscopy, mass spectrometry, and elemental analysis. The structure of [Ru(IV)(TTP)(NH-p-C6H4Cl)2 . CH2Cl2 was determined by X-ray crystallography. The Ru-N bond length and the Ru-N-C angle of the Ru-NHAr moiety are 1.956(7) A and 135.8(6) degrees, respectively.     

Synthese eines Titana-Oxacyclohexanringes durch kontrollierte Ringöffnung von Tetrahydrofuran. Kristallstrukturen von [Ti(CH2)4O{Me2Si(NBut)2}]2, [TiCl{Me2Si(NBut)2}]3(μ3-O)(μ3-Cl) und [Li2(THF)3{Me2Si(NBut)2}]

Synthesis of a Titana-Oxacyclohexane Ring by Controlled Ring Opening of Tetrahydrofurane. Crystal Structures of [Ti(CH₂)₄O{Me₂Si(NBu^t)₂}]₂, [TiCl{Me₂Si(NBu^t)₂}]₃(μ₃-O)(μ₃-Cl), and [Li₂(THF)₃{Me₂Si(NBu^t)₂}] [TiCl₃(THF)₃] reacts with [(Bu^tNLi)₂SiMe₂]₂ in diethyl ether at –35 °C under redox disproportionation and formation of the yellow titana(IV)-oxacyclohexane complex [Ti(CH₂)₄O{Me₂Si(NBu^t)₂}]₂. According to the crystal structure analysis the titanium atoms are linked to form centrosymmetric dimers via the oxygen atoms of the Ti(CH₂)₄O six-membered rings, which are in chair conformation. Along with the nitrogen atoms of the chelating [Me₂Si(NBu^t)₂]^2– ligands the titanium atoms obtain a distorted trigonal-bipyramidal surrounding. While [TiCl{Me₂Si(NBu^t)₂}]₃(μ₃-O)(μ₃-Cl) with a cluster-like structure is obtained as a by-product. According to the crystal structure analysis of [Li₂(THF)₃ · {Me₂Si(NBu^t)₂}], which is involved in the synthesis reaction, the two lithium atoms are connected with both the nitrogen atoms of the t-butyl amide groups and bridged via an oxygen atom of one of the THF molecules.     

One-pot synthesis of metal primary phosphine complexes from O=PCl2R or PCl2R. Isolation and characterization of primary alkylphosphine complexes of a metalloporphyrin

Treatment of [Ru(II)(Por)(CO)] [Por = porphyrinato(2-)] and O=PCl(2)R [R = Ad (adamantyl), Bu(t), Bu(sec)] or PCl2Mes (Mes = mesityl) with LiAlH4 afforded primary alkyl- and arylphosphine complexes [Ru(II)(Por)(PH2R)2], which have been isolated in pure form and characterized by 1H NMR, 31P NMR, IR, and UV-vis spectroscopy and mass spectrometry. The structures of [Ru(II)(TTP)(PH2Ad)2] and [Ru(II)(F20-TPP)(PH2Mes)2] were determined by X-ray crystallography.     

Intramolecular C-N bond formation reactions catalyzed by ruthenium porphyrins: amidation of sulfamate esters and aziridination of unsaturated sulfonamides

Ruthenium porphyrins [Ru(F(20)-TPP)(CO)] (F(20)-TPP = 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato dianion) and [Ru(Por*)(CO)] (Por = 5,10,15,20-tetrakis[(1S,4R,5R,8S)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanoanthracen-9-yl]porphyrinato dianion) catalyzed intramolecular amidation of sulfamate esters p-X-C(6)H(4)(CH(2))(2)OSO(2)NH(2) (X = Cl, Me, MeO), XC(6)H(4)(CH(2))(3)OSO(2)NH(2) (X = p-F, p-MeO, m-MeO), and Ar(CH(2))(2)OSO(2)NH(2) (Ar = naphthalen-1-yl, naphthalen-2-yl) with PhI(OAc)(2) to afford the corresponding cyclic sulfamidates in up to 89% yield with up to 100% substrate conversion; up to 88% ee was attained in the asymmetric intramolecular amidation catalyzed by [Ru(Por)(CO)]. Reaction of [Ru(F(20)-TPP)(CO)] with PhI[double bond]NSO(2)OCH(2)CCl(3) (prepared by treating the sulfamate ester Cl(3)CCH(2)OSO(2)NH(2) with PhI(OAc)(2)) afforded a bis(imido)ruthenium(VI) porphyrin, [Ru(VI)(F(20)-TPP)(NSO(2)OCH(2)CCl(3))(2)], in 60% yield. A mechanism involving reactive imido ruthenium porphyrin intermediate was proposed for the ruthenium porphyrin-catalyzed intramolecular amidation of sulfamate esters. Complex [Ru(F(20)-TPP)(CO)] is an active catalyst for intramolecular aziridination of unsaturated sulfonamides with PhI(OAc)(2), producing corresponding bicyclic aziridines in up to 87% yield with up to 100% substrate conversion and high turnover (up to 2014).     

Tuning the reactivity of dioxoruthenium(VI) porphyrins toward an arylimine by altering porphyrin substituents

Reaction of dioxoruthenium(VI) porphyrins [Ru(VI)(Por)O2] with arylimine HN=CPh2 in dichloromethane afforded bis(methyleneamido)ruthenium(IV) porphyrins [Ru(IV)(Por)(N=CPh2)2] for Por = 4-Cl-TPP and TMP; (methyleneamido)hydroxoruthenium(IV) porphyrins [Ru(IV)(Por)(N=CPh2)(OH)] for Por = TPP and TTP; and bis(arylimine)ruthenium(II) porphyrins [Ru(II)(Por)(HN=CPh2)2] for Por = 3,5-Cl2TPP and 3,5-(CF3)2TPP. In dichloromethane solution exposed to air, complex [Ru(II)(3,5-Cl2TPP)(HN=CPh2)2] underwent oxidative deprotonation to form [Ru(IV)(3,5-Cl2TPP)(N=CPh2)2]. The new ruthenium porphyrins were identified by 1H NMR, UV-vis, IR, and mass spectroscopy, along with elemental analysis. X-ray crystal structure determinations of [Ru(IV)(4-Cl-TPP)(N=CPh2)2], [Ru(IV)(TPP)(N=CPh2)(OH)], and [Ru(II)(3,5-(CF3)2TPP)(HN=CPh2)2] revealed the Ru-N(methyleneamido) or Ru-N(arylimine) distances of 1.897(5) A (average), 1.808(4) A, and 2.044(2) A (average), respectively.     

Synthesis and characterization of aluminum(III) and tin(II) complexes supported by diiminophosphinate ligands and their application in ring‐opening polymerization catalysis of ε‐caprolactone

A series of Al(III) and Sn(II) diiminophosphinate complexes have been synthesized. Reaction of Ph(ArCH₂)P(?NBu^t)NHBu^t (Ar = Ph, 3 ; Ar = 8‐quinolyl, 4 ) with AlR₃ (R = Me, Et) gave aluminum complexes [R₂Al{(NBu^t)₂P(Ph)(CH₂Ar)}] (R = Me, Ar = Ph, 5 ; R = Me, Ar = 8‐quinolyl, 6 ; R = Et, Ar = Ph, 7 ; R = Et, Ar = quinolyl, 8 ). Lithiated 3 and 4 were treated with SnCl₂ to afford tin(II) complexes [ClSn{(NBu^t)₂P(Ph)(CH₂Ar)}] (Ar = Ph, 9 ; Ar = 8‐quinolyl, 10 ). Complex 9 was converted to [(Me₃Si)₂NSn{(NBu^t)₂P(Ph)(CH₂Ph)}] ( 11 ) by treatment with LiN(SiMe₃)₂. Complex 11 was also obtained by reaction of 3 with [Sn{N(SiMe₃)₂}₂]. Complex 9 reacted with [LiOC₆H₄Bu^t‐4] to yield [4‐Bu^tC₆H₄OSn{(NBu^t)₂P(Ph)(CH₂Ph)}] ( 12 ). Compounds 3–12 were characterized by NMR spectroscopy and elemental analysis. The structures of complexes 6 , 10 , and 11 were further characterized by single crystal X‐ray diffraction techniques. The catalytic activity of complexes 5–8 , 11 , and 12 toward the ring‐opening polymerization of ε‐caprolactone (CL) was studied. In the presence of BzOH, the complexes catalyzed the ring‐opening polymerization of ε‐CL in the activity order of 5 > 7 ≈ 8 > 6 ? 11 > 12 , giving polymers with narrow molecular weight distributions. The kinetic studies showed a first‐order dependency on the monomer concentration in each case. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4621–4631, 2006     

Molybdenum(VI) Bis(imido) Complexes: From Frustrated Lewis Pairs to Weakly Coordinating Cations

Molybdenum(VI) bis(imido) complexes [Mo(NtBu)₂(L^R)₂] (R=H 1 a ; R=CF₃ 1 b ) combined with B(C₆F₅)₃ ( 1 a /B(C₆F₅)₃, 1 b /B(C₆F₅)₃) exhibit a frustrated Lewis pair (FLP) character that can heterolytically split H−H, Si−H and O−H bonds. Cleavage of H₂ and Et₃SiH affords ion pairs [Mo(NtBu)(NHtBu)(L^R)₂][HB(C₆F₅)₃] (R=H 2 a ; R=CF₃ 2 b ) composed of a Mo(VI) amido imido cation and a hydridoborate anion, while reaction with H₂O leads to [Mo(NtBu)(NHtBu)(L^R)₂][(HO)B(C₆F₅)₃] (R=H 3 a ; R=CF₃ 3 b ). Ion pairs 2 a and 2 b are catalysts for the hydrosilylation of aldehydes with triethylsilane, with 2 b being more active than 2 a . Mechanistic elucidation revealed insertion of the aldehyde into the B−H bond of [HB(C₆F₅)₃]⁻. We were able to isolate and fully characterize, including by single-crystal X-ray diffraction analysis, the inserted products Mo(NtBu)(NHtBu)(L^R)₂][{PhCH₂O}B(C₆F₅)₃] (R=H 4 a ; R=CF₃ 4 b ). Catalysis occurs at [HB(C₆F₅)₃]⁻ while [Mo(NtBu)(NHtBu)(L^R)₂]⁺ (R=H or CF₃) act as the cationic counterions. However, the striking difference in reactivity gives ample evidence that molybdenum cations behave as weakly coordinating cations (WCC).     

The tris(triphenylphosphine)osmium zerovalent complexes Os(CO)2(PPh3)3, .Os(CO)(CNR)(PPh3)3, Os(CO)(CS)(PPh3)3, Os(CS)(cNR)(PPh3)3 and derived compounds

Detailed procedures for the syntheses of Os(CO)₂(PPh₃)₃, Os(CO)(CNR)-(PPh₃)₃ (R = p-tolyl), Os(CO)(CS)(PPh₃)₃ and Os(CS)(CNR)(PPh₃)₃, together with the derived complexes Os(CO)₂(CS)(PPh₃)₂, Os(CO)(CS)(CNR)(PPh₃)₂, Os(η²-C₂H₄)(CO)(CNR)(PPh₃)₂, Os(η²-C₂H₄)(CO)(CS)(PPh₃)₂, Os(η²CS₂)(CO)₂-(PPh₃)₂, Os(η²CS₂)(CO)(CS)(PPh₃)₂, Os(η²-CS₂)(CO)(CNR)(PPh₃)₂, Os(η²PhC₂Ph)(CO)₂(PPh₃)₂ and OsH(C2Ph)(CO)₂(PPh₃)₂ are described.     

The X-ray structure of Os(CS)(PhCCPh)(PPh3)2, a complex containing a four-electron donor acetylene ligand

Os(CS)(PhC?CPh)(PPh₃)₂ is formed by the treatment of Os(CS)(CO)(PPh₃)₃ with diphenylacetylene and is an example of a complex containing a four-electron donor acetylene ligand. Os(CS)(PhC?CPh)(PPh₃)₂ crystallizes in the monoclinic space group P2₁/n with the cell dimensions a = 9.028(5), b = 25.256(2) and c = 19.22(2) Å with β = 103.8(7)°, V = 4260 ų, Z = 4 and d(calcd) = 1.461 g cm^?3 for mol.wt 937.09 g mol^?1. Diffraction data were collected with a Nonius CAD-4 diffractometer and refined to R = 4.05% and R_w = 4.19% for 1172 independent reflections. The structure can be described as a distorted trigonal bipyramid with the CS ligand occupying an axial position. The two cis-PPh₃ ligands are in equatorial sites with the acetylene occupying a position between the remaining axial and equatorial sites. The diphenylacetylene is symmetrically bound to the metal with an average Os? C distance of 2.04(3) Å. The Os? CS distance is unusually short at 1.79(2) Å.     

Bis axial ligation of simple imine and methyleneamido groups by ruthenium porphyrins

Bis(N-ethylideneethanamine)ruthenium(ii) porphyrins, [Ru11(Por)(N(Et)=CHMe)2] (Por=TTP, 4-Cl-TPP), were prepared by the reaction of dioxoruthenium(VI) porphyrins with triethylamine in approximately 85% yields. The reaction between dioxoruthenium(VI) porphyrins and benzophenone imine afforded bis(diphenylmethyleneamido)ruthenium(IV) porphyrins, [Ru(IV)(Por)(N=CPh2)2] (Por=TTP, 3,4,5-MeO-TPP), in approximately 65% yields. These new classes of metalloporphyrins were characterized by 1H NMR, UV/Vis, and IR spectroscopy as well as by mass spectrometry and elemental analysis. The X-ray crystallographic structures of [Ru(II)(TTP)(N(Et)=CHMe)2] and [Ru(IV)(3,4,5-MeO-TPP)(N=CPh2)2] revealed an axial Ru-N bond length of 2.115(6) A for the imine complex and 1.896(8) A for the methyleneamido complex. Each of the N=CPh2 axial groups in [Ru(IV)(3,4,5-MeO-TPP)(N=CPh2)2] adopts a linear coordination mode with a corresponding Ru-N-C angle of 175.9(9)degrees. Spectral and structural studies revealed essentially single bonding character for the bis(imine) complexes but a multiple bonding character for the bis(methyleneamido) complexes with respect to their axial Ru-N bonds.     

Vibrational spectra of mixed (phthalocyaninato)(porphyrinato) yttrium(III) double-decker complexes: Density functional theory calculations

The vibrational (IR and Raman) spectra of neutral and reduced mixed (phthalocyaninato)(porphyrinato) yttrium(III) double-decker complexes Y(Pc)(Por) and [Y(Pc)(Por)]⁻ [the simplified models of mixed (phthalocyaninato)(porphyrinato) rare earth(III) complexes] are studied using density functional theory (DFT) calculations. The simulated IR and Raman spectra of Y(Pc)(Por) are compared with the experimental IR spectrum of Tb(Pc)(TClPP) and Raman spectrum of Y(Pc)(TClPP), respectively, and many bands can acceptably fit in spite of the different species. On the basis of comparison with the simulated spectra of PbPc and PbPor together with the assistance of normal coordinate analysis, the calculated frequencies in their IR and Raman spectra are identified in terms of the vibrational mode of different ligand for the first time. The calculated frequency at 1048 cm⁻¹ in the IR spectrum of [Y(Pc)(Por)]⁻ with contribution from both Pc and Por vibrational modes is the characteristic IR vibrational mode of the reduced double-decker, while the characteristic IR vibrational mode of Y(Pc)(Por) attributed from the vibration of phthalocyanine monoanion radical Pc⁻ appears at 1257 cm⁻¹. In line with our previous experimental findings that the Raman spectra of M(Pc)(TPP) and M(Pc)(TClPP) are dominated by the Pc vibrational modes, theoretical calculations indicate that most of the Raman vibrational modes contributed from Por ring are covered up by those of Pc ring and thus are hard to be recognized in the Raman spectra of [Y(Pc)(Por)]⁻ and Y(Pc)(Por) due to their much weaker intensity in comparison with that of Pc ligand. Comparison in the IR and Raman spectra between [Y(Pc)(Por)]⁻ and Y(Pc)(Por) also suggests the localization of hole on the Pc ring in the neutral double-decker Y(Pc)(Por). The present work, representing the first detailed DFT study on the vibrational spectra of mixed (phthalocyaninato)(porphyrinato) rare earth(III) double-decker complexes, is useful in helping to understand the vibrational spectroscopic properties of this series of mixed tetrapyrrole ring complexes.     

Characterization and structure of OsH(OH)(CO)(PtBu2Me)2

A synthesis of the title compound by hydrolysis of OsH(C₆H₅)(CO)(P^tBu₂Me)₂ has the advantage that the product shows ¹H NMR spectra free of the influence of hydrogen bonding to water impurity. In the solid state, the hydroxyl group interacts weakly with that of a neighbor. The Os–OH bond is rapidly split by H₂, to give H₂O and Os(H)₂(H₂)(CO)(P^tBu₂Me)₂.     

The polymer [OsCl2 (cod)]x as a route to hydrazine- and hydrazone-osmium(II) complexes; The crystal structure of [Os(cod)(CNBut)2(NH2NCMe2)2] (BPh4)2·(acetone)2

The salts, [OsCl(cod)(NH₂NR₂)₃]X (R = H, X = BPh₄; R = Me, X = PF₆) and [Os(cod)(NH₂NH₂)₄](BPh₄)₂, formed from [OsCl₂(cod)]_x and hydrazines, can be converted into a range of hydrazine- and hydrazone-osmium(II) complexes with isocyanides and tertiary phosphorus ligands. The crystal structure of [Os(cod)(CNBu^t)₂(NH₂NCMe₂)₂](BPh₄)₂·(acetone)₂ has been elucidated.     

Cluster chemistry: XVI. Synthesis and crystal structure of AuFe3(μ3-HCNBut)(CO)9(PPh3), an AuFe3 butterfly cluster

The reaction between AuCl(PPh₃ and [Fe(μ₃-HCNBu^t)(CO)₉]^? gives AuFe₃(μ₃-HCNBu^t)(CO)₉(PPh₃), crystals of which are triclinic, space group P$\text{1}$, with a 12.815(3), b 16.265(4), c 19.106(3) Å, α 67.15(3), β 73.46(2), γ 73.12(2)° and Z = 4. The comlex contains an AuFe₃ “butterfly” cluster, the Fe₃ face of which is bridged by the HCNBu^t ligand bonded in the (2σ + π) mode on the side opposite to the Au(PPh₃) moiety, which, contrary to expectation based on the analogy with H, bridges the two Fe atoms σ-bonded to N, and π-bonded to the CN group. The AuFe₂/Fe₃ dihedral angles in the two independent molecules differ significantly, with values of 110.9 and 132.1°.     

Synthese und Kristallstruktur von Tetraphenylphosphonium-Aquabis(tetrasulfido)thionitrosyl-Osmat,PPh4[Os(NS)(S4)2(H2O)]

Synthesis and Crystal Structure of Tetraphenylphosphonium Aqua-bis(tetrasulfido)thionitrosyl Osmate, PPh₄[Os(NS)(S₄)₂(H₂O)] PPh₄[Os(NS)(S₄)₂(H₂O)] has been prepared as redbrown crystals by reacting PPh₄[OsNCl₄] with a solution of excess disodium tetrasulfide in dimethylformamide/H₂O and characterized by IR spectroscopy and by a crystal structure determination. Space group P2₁/n, Z = 4, structure solution with 4162 independent reflections, R = 0.059 for reflections with I > 2σ(I). Lattice dimensions at ?40°C: a = 1138.9(5), b = 1301.4(4), c = 2092.7(7) pm, β = 104.74(3)º. Os? N, Os? O, and Os? S distances are 175.2(12), 219.8(12), and 237.5(4)?239.1(4) pm, respectively. The Os?N?S moiety is approximately linear, with an OsNS angle of 171.2(7)º.     

Complexes of Co(II) and Zn(II) with N-(Thio)phosphorylthioureas AdNHC(S)NHP(O)(OiPr)2 and MeNHC(S)NHP(S)(OiPr)2

The reaction of the potassium salt of the N-(thio)phosphorylated thioureas AdNHC(S)NHP(O)(OiPr)₂ (HL^I , Ad = Adamantyl) and MeNHC(S)NHP(S)(OiPr)₂ (HL^II ) with Co(II) and Zn(II) in aqueous EtOH leads to [ML^I,II ₂] chelate complexes. They were investigated by UV-vis, ¹H and ³¹P NMR spectroscopy, and microanalysis. The molecular structures of [ML^I ₂] were elucidated by single crystal X-ray diffraction analysis. The metal centers in both complexes are found to be in a distorted-tetrahedral O₂S₂ environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated L^I ligands. The photoluminescence properties of [ZnL^II ₂] are also reported.     

Synthesis and Structure of Two Isomers of Re2Os2(CO)14(CNBu t )4: Clusters with Linear ReOs2Re Chains

The complexes (OC)₄(CNBu ^t )ReOs(CO)₃(CNBu ^t )Os(CO)₃(CNBu ^t )Re(CNBu ^t )(CO)₄ (A) and (OC)₃(CNBu ^t )₂ReOs(CO)₄Os(CO)₃(CNBu ^t )Re(CNBu ^t )(CO)₄ (B) have been isolated in low yield from the reaction of Os(CO)₃(CNBu ^t )₂ with Re₂(-H)(--C₂H₃)(CO)₈ in hexane at room temperature. Both compounds have approximately linear ReOs₂Re chains. The Re–Os lengths are in the range 2.9311(7)–2.952(1) Å the Os–Os lengths are 2.875(1) (A) and 2.8759(7) Å (B).     

Heterodinukleare Komplexe: Synthese und Kristallstrukturen von [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)], [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)]

Heterobinuclear Complexes: Synthesis and X‐ray Crystal Structures of [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)], [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)], and [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] [Ru₃Rh(CO)₇(μ₃‐H)(μ‐P^tBu₂)₂(^tBu₂PH)(μ‐Cl)₂] ( 2 ) yields by cluster degradation under CO pressure as main product the heterobinuclear complex [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)] ( 4 ). The compound crystallizes in the orthorhombic space group Pcab with a = 15.6802(15), b = 28.953(3), c = 11.8419(19) Å and V = 5376.2(11) ų. The reaction of 4 with dppm (Ph₂PCH₂PPh₂) in THF at room temperature affords in good yields [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐dppm)] ( 7 ). 7 crystallizes in the triclinic space group P 1 with a = 9.7503(19), b = 13.399(3), c = 15.823(3) Å and V = 1854.6 ų. Moreover single crystals of [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 9 ) could be obtained and the single‐crystal X‐ray structure analysis revealed that 9 crystallizes in the monoclinic space group P2₁/a with a = 11.611(2), b = 13.333(2), c = 18.186(3) Å and V = 2693.0(8) ų.