Synthesis of cis-(Me3Sn)2Fe(CO)4 by reaction of (Me3Sn)3Sb with Fe2(CO)9. Formation of (Me3E)3SbFe(CO)4 (E = Si,Ge)

(Me₃Sn)₃Sb and Fe₂(CO)₉ reacted to form (Me₃Sn)₂Fe(CO)₄ in 79% yield. From (Me₃E)₃Sb(E = Si or Ge) and Fe₂(CO)₉ the complexes (Me₃E)₃SbFe(CO)₄ were obtained     

Ligand substitution in cubic clusters: surprising isolation of the cocrystallization products of Cu8(mu8-Se)[S2P(OEt)2]6 and Cu6[S2P(OEt)2]6

The cluster (Cu8(mu8-Se)[S2P(OEt)2]6)0.54(Cu6[S2P(OEt)2]6)0.46 (2) was prepared in 78% yield from the reaction of Cu8(Se)[Se2P(OPr)2]6 (1) and NH4S2P(OEt)2 in toluene. The central selenide ion in 2 was characterized by 77Se NMR at delta -976 ppm. The simulated solid-state 31P NMR spectrum shows two components with an intensity ratio close to 55:45. The peak centered at 100.7 ppm is assigned to the 31P nuclei in the hexanuclear copper cluster, and that at 101.1 ppm is due to the octanuclear copper cluster. The single-crystal X-ray diffraction analysis confirms the cocrystallization structures of Cu8(Se)[S2P(OEt)2]6 (54%) and Cu6[S2P(OEt)2]6 (46%) (2: trigonal, space group R3, a=21.0139(13) A, c=11.404(3) A, gamma=120 degrees, Z=3). While the octanuclear copper cluster possesses a 3-fold crystallographic axis which pass through the Cu2, Se, and Cu(2A) atoms, the six copper atoms having the S6 point group symmetry in Cu6[S2P(OEt)2]6 form a compressed octahedron. The Cu8(mu8-Se) cubic core in Cu8(mu8-Se)[S2P(OEt)2]6 is larger in size than the metal core in Cu8(mu8-Se)[Se2P(OPr)2]6 (1) although the bite distance of the Se-containing bridging ligand is larger than that of the S ligand. To understand the nature of the structure contraction of the metal core and metal-mu8-Se interaction, molecular orbital calculations have been carried out at the B3LYP level of density functional theory. MO calculations suggest that Cu-mu8-Se interactions are not very strong and a half bond can be formally assigned to each Cu-mu8-Se bond. Moderate Cu...Cu repulsion exists, and it is the bridging ligands that are responsible for the observed Cu...Cu contacts. Hence, the S-ligating copper clusters have greater Cu...Cu separations because each Cu carries more positive charge in the presence of the more electronegative S-containing ligands.     

Pentasulfide S5(2-) as the first tridentate chelating ligand in Ru(P(OE)3)3S5(E = Me and Et)

Room temperature stirring of H2Ru(P(OE)3)4 (E = Me and Et) and elemental sulfur in benzene afforded the optically active compounds Ru(P(OMe)3)3S5 (1) and Ru(P(OEt)3)3S5 (2). Compounds 1 and 2 are crystallized in the trigonal space group P31 with a = 14.231(10) A, c = 10.24(1) A, V = 1794(2) A3, and Z = 3, and orthorhombic space group P212121 with a = 15.393(5) A, b = 18.126(6) A, c = 12.421(4) A, V = 3465(1) A3, and Z = 4, respectively. Solutions of 1 and 2 did not show any optical activity since the bulk materials are racemic mixtures. The X-ray analyses also reveal that in both compounds polysulfide S5(2-) ion acts as a novel tridentate ligand, resulting in an asymmetric bicyclic RuS5 unit having three- and five-membered rings around the ruthenium atom. Fragmentation of the S5(2-) ring to S2- ion was observed in the presence of sulfur-abstracting reagents such as PR3 (R = Ph, OMe, and OEt) and also to S2(2-) ion when the compounds were reacted with RuCl2(P(OE)3)4 (E = Me and Et).     

[Co4P2(PtBu2)2(CO)8] und [{Co(CO)3}2P4tBu4] aus Co2(CO)8 und tBu2P–P=P(Me)tBu2

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XIX. [Co₄P₂(P^tBu₂)₂(CO)₈] and [{Co(CO)₃}₂P₄^tBu₄] from Co₂(CO)₈ and ^tBu₂P–P=P(Me)^tBu₂ Co₂(CO)₈ reacts with ^tBu₂P–P=P(Me)^tBu₂ yielding the compounds [Co₄P₂(P^tBu₂)₂(CO)₈] ( 1 ) and [{η^2tBu₂P=P–P=P^tBu₂}{Co(CO)₃}₂] ( 2 a ) cis, ( 2 b ) trans. In 1 , four Co and two P atoms form a tetragonal bipyramid, in which two adjacent Co atoms are μ₂‐bridged by ^tBu₂P groups. Additionally, two CO groups are linked to each Co atom. In 2 a and 2 b , each of the Co(CO)₃ units is η²‐coordinated to the terminal P₂ units resulting in the cis‐ and trans‐configurations 2 a and 2 b . 1 crystallizes in the orthorhombic space group Pnnm (No. 58) with a = 879,41(5), b = 1199,11(8), c = 1773,65(11) pm. 2 a crystallizes in the monoclinic space group P2₁/n (No. 14) with a = 875,97(5), b = 1625,36(11), c = 2117,86(12) pm, β = 91,714(7)°. 2 b crystallizes in the triclinic space group P 1 (No. 2) with a = 812,00(10), b = 843,40(10), c = 1179,3(2) pm, α = 100,92(2)°, β = 102,31(2)°, γ = 102,25(2)°.     

The spin coupling in the diiron complex [Fe2(hpdta)(H2O)3Cl

Density functional, multireference configuration interaction, and modified valence configuration interaction calculations are used to investigate the electronic structure and spin coupling of the dinuclear [Fe(2)(hpdta)(H(2)O)(3)Cl] complex (H(5)hpdta = Hydroxypropane-1,3-diamine-N,N,N',N'-tetraacetic acid). The density functional calculations give evidence of both, states with local high-spin iron centres and states with local low-spin iron centres, the relative energy of which strongly depends on the functional. The splitting of states due to the spin coupling between the high-spin iron centres varies by more than a factor of two for different functionals. In an attempt to study to what extent it is possible to undertake configuration interaction calculations on such binuclear compounds, multireference configuration interaction calculations are performed on a [Fe(2)(OH)(5)(H(2)O)(3)(NH(3))(2)Cl] model complex. The results show that, when correlating only the ten iron 3d orbitals and the four valence orbitals of the bridging OH group, the calculated splitting is still by a factor of about 3 smaller than the value for the splitting inferred from magnetic susceptibility measurements. Modified valence configuration interaction calculations are performed to approximately take into account the influence of orbital relaxation effects of all occupied orbitals in the excited configurations. The exchange splitting is significantly increased, but still smaller than the experimental value.     

CRYSTAL STRUCTURE OF Mo_3(μ3-S)(μ-S)_2[S_2P(OEt)_2]_3][SOP(OEt)_2](0)_2

<正> M=1140.85, monoclinic, P21/c. a=12.748(2), b=14.320(2), c=23.118 (3)A,β=101.07(1)°, V=4141(2)A3, Z=4, Dc=1.830 g.cm-3. Final R=0.039 for 4160 reflections.The title compound is a rather irregular trinuclear molybdenum cluster having only two M-M bonds with two shorter Mo-Mo distances of 2.808(1), 2.839(1), and one longer Mo-Mo distance of 3.337(1)8. The existence of two Mo-Mo bonds is coincident with the electron counting for {Mo3} cluster core, and may be regarded as a result of the oxidation of a compound Mo3(μ3-S)(μ-S)2 (μ-L)[S2P(OEt)2]4(L') (L'=neutral ligands)1 characterized by us previously.     

Synthesis and structural characterization of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH3CO2)Mn(CO)2[P(C6H5)3]2: An organometallic complex containing a chelating acetate ligand

The accidental but intriguing synthesis of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH₃CO₂)Mn(CO)₂[P(C₆H₅)₃]₂, has been accomplished by the reaction of NaMn(CO)₅ with (CH₃)₃SiCl followed by the addition of triphenylphosphine and acetic acid. A three-dimensional single-crystal X-ray diffraction analysis has shown an octahedral-like molecule containing a symmetrically oxygen-chelating acetate group, the first such group to be reported in a metal carbonyl complex. The two triphenylphosphine ligands occupy mutually trans positions with the two carbonyl ligands possessing the remaining cis sites in the octahedral complex. The compound crystallizes with four molecules in a monoclinic unit cell of space group symmetry $\text{P}\text{2}{}_1\text{c}$ and of dimensions a = 17.744(2) Å, b = 9.692(1) Å, c = 20.004(2) Å, and β = 106.195(4)°. The relatively long MnO(acetate) bond lengths [2.066(6) and 2.069(7) Å] and the relatively short MnCO bond lengths [1.701(12) and 1.760(13) Å] and the relatively short MnP(C₆H₅)₃ bond lengths [2.260(3) and 2.275(3) Å], compared to the corresponding MnCO and MnP(C₆H₅)₃ bond lengths in other manganese carbonyl triphenylphosphine complexes, are rationalized on the basis that the acetate ligand in this molecule functions primarily as a σ-donor.     

Reactions of IrHCl2(PPh3)2{P(OEt)3} with Organic Azides: Formation of Aminophosphonium Salts

Aminophosphonium salts [Ph₃PN(H)R]BPh₄ ( 1 ) [R = C₆H₅CH₂ ( 1a ), 4‐CH₃C₆H₄CH₂ ( 1b ), C₆H₅ ( 1c )] were obtained by allowing hydride IrHCl₂(PPh₃)₂{P(OEt)₃} to react first with triflic acid and then with the organic azide RN₃. The compounds were characterized spectroscopically and by X‐ray crystal structure determination of [Ph₃PN(H)CH₂C₆H₄‐4‐CH₃]BPh₄ ( 1b ). A reaction path for the formation of aminophosphonium cations is also proposed.     

Picosecond X-ray absorption measurements of the ligand substitution dynamics of Fe(CO)5 in ethanol

Ultrafast X-ray absorption near edge spectroscopy has been carried out for photo excited iron pentacarbonyl in ethanol with 2 picosecond resolution. A temporal resolution limited dissociation process was observed, followed by the formation of the mono-substituted complex Fe(CO)(4)EtOH within a few tens of picoseconds. The measurements have been carried out with a newly developed X-ray absorption instrument at station 7 ID-C of the Advanced Photon Source. The results show that single picosecond temporal resolution can be achieved at a synchrotron beam line.     

Reduction products of dinuclear [Rh2Cl2(CO)2 {μ-(PhO)2PN(Et)P(OPh)2}2]. Crystal structure of [Rh2HgCl(μ-H)(CO)2 {μ-(PhO)2PN(Et)P(OPh)2}2]

Treatment of [Rh₂Cl₂(CO)₂ {μ-(PhO)₂PN(Et)P(OPh)₂}₂] with various reducing agents gives a number of products, the type depending on the conditions employed. The products isolated include [Rh₂(CO)₂{μ-(PhO)₂PN(Et)P(OPh)₂}₂], [Rh₂(CO)₃{μ-(PhO)₂PN(Et)P(OPh)₂}₂],and [Rh₂HgCl(μ-H)(CO)₂{μ-(PhO)₂PN(Et)P(OPh)₂}₂]; the structure of the last complex was determined by X-ray diffraction.     

A novel amido–pyrophosphate MnII chelate complex with the synthetic ligand O{P(O)[NHC(CH3)3]2}2 (L): [Mn(L)2{OC(H)N(CH3)2}2]Cl2·2H2O

The title complex, trans‐bis(dimethylformamide‐κO)bis{N,N′‐N′′,N′′′‐tetra‐tert‐butyl[oxybis(phosphonic diamide‐κO)]}manganese(II) dichloride dihydrate, [Mn(C₁₆H₄₀N₄O₃P₂)₂(C₃H₇NO)₂]Cl₂·2H₂O, is the first example of a bis‐chelate amido–pyrophosphate (pyrophosphoramide) complex containing an O[P(O)(NH)₂]₂ fragment. Its asymmetric unit contains half of the complex dication, one chloride anion and one water molecule. The Mn^II atom, located on an inversion centre, is octahedrally coordinated, with a slight elongation towards the monodentate dimethylformamide ligand. Structural features of the title complex, such as the P=O bond lengths and the planarity of the chelate ring, are compared with those of previously reported complexes with six‐membered chelates involving the fragments C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)₂ and P(O)] and O[P(O)(N)₂]₂. This analysis shows that the six‐membered chelate rings are less puckered in pyrophosphoramide complexes containing a P(O)OP(O) skeleton, such as the title compound. The extended structure of the title complex involves a linear aggregate mediated by N—H...O and N—H...Cl hydrogen bonds, in which the chloride anion is an acceptor in two additional O—H...Cl hydrogen bonds.     

Die Reaktion von tBu2P‐P=P(Me)tBu2 mit [Fe2(CO)9] und [(η2‐C8H14)2Fe(CO)3]

^tBu₂P‐P=P(Me)^tBu₂ reacts with [Fe₂(CO)₉] to give [μ‐(1, 2, 3:4‐η‐^tBu₂P¹‐P²‐P³‐P^4tBu₂){Fe(CO)₃}{Fe(CO)₄}] ( 1 ) and [trans‐(^tBu₂MeP)₂Fe(CO)₃]( 2 ). With [(η²‐C₈H₁₄)₂Fe(CO)₃] in addition to [μ‐(1, 2, 3:4‐η‐^tBu₂P¹‐P²‐P³‐P^4tBu₂){Fe(CO)₂PMe^tBu₂}‐{Fe(CO)₄}] ( 10 ) and 2 also [(μ‐P^tBu₂){μ‐P‐Fe(CO)₃‐PMe^tBu₂}‐{Fe(CO)₃}₂(Fe‐Fe)]( 9 ) is formed. 1 crystallizes in the monoclinic space group P2₁/c with a = 875.0(2), b = 1073.2(2), c = 3162.6(6) pm and β = 94.64(3)?. 2 crystallizes in the monoclinic space group P2₁/c with a = 1643.4(7), b = 1240.29(6), c = 2667.0(5) pm and β = 97.42(2)?. 9 crystallizes in the monoclinic space group P2₁/n with a = 1407.5(5), b = 1649.7(5), c = 1557.9(16) pm and β = 112.87(2)?.     

Electronic and Steric Structure of the Methanofullerene C61(CO2Me)[P(O)(OMe)2]. A Density Functional Study

The asymmetric addend in the methanofullerene C₆₁(CO₂Me)[P(O)(OMe)₂] polarizes and divides the fullerene shell into four nonequivalent fragments. According to DFT/PBE calculations, the most stable conformers of the methanofullerene C₆₁(CO₂Me)[P(O)(OMe)₂] involve Coulomb interactions of the phosphoryl oxygen with one of the fullerene carbon atoms, which produces polarization of the corresponding fragment and asymmetry in bond lengths and atomic charges in the fullerene shell. Alternation and attenuation of changes in bond lengths along the conjugation branches was revealed.     

Reactions of Distibanes with [Fe2(CO)9]: Synthesis,Structure and DFT Calculations of [(Et2Sb)4Fe4(CO)14], [(nPr2Sb)4Fe3(CO)10], [{(Me3SiCH2)2Sb}4Fe2(CO)6], and [2‐(Me2NCH2)C6H4SbFe2(CO)8]

The iron complexes [(Et₂Sb)₄Fe₄(CO)₁₄] ( 1 ), [(nPr₂Sb)₄Fe₃(CO)₁₀] ( 2 ), [{(Me₃SiCH₂)₂Sb}₄Fe₂(CO)₆] ( 3 ), and [2‐(Me₂NCH₂)C₆H₄SbFe₂(CO)₈] ( 4 ) were prepared by reactions of distibanes with Fe₂(CO)₉. Compounds 1 – 4 were characterized by X‐ray diffraction, ¹H NMR and IR spectroscopy as well as mass spectrometry; complex 1 was additionally characterized by density functional calculations.     

Synthesis and characterization of thio-bis(t-butylphosphido) diiron hexacarbonyls,Fe2(CO)6(butP)2Sx (x = 2, 3). Molecular structure of Fe2(CO)6(ButPS2PBut)

Two isomers of dithio-bis(t-butylphosphido)diiron hexacarbonyl, Fe₂(CO)₆(Bu^tP)₂S₂, and trithio-bis(t-butylphosphido)diiron hexacarbonyl, Fe₂(CO)₆(Bu^tP)₂S₃ were isolated from the reaction of the lithio compound Fe₂(CO)₆(bu^tPLi)₂ with sulfur monochloride, S₂Cl₂ at − 10°C. The new complexes were characterized by IR, ¹H NMR and mass spectra and elemental analysis. The crystal and molecular structure of Fe₂(CO)₆(Bu^tPS₂PBu^t) (I) was determined by single crystal X-ray diffraction. Compound I crystallises in the orthorhombic system, space group Pna2₁ with a 2433.1(3), b 906.75(8), c 973.43(7) pm; Z = 4; d_calc 1.61 g cm⁻³; R₁ = 0.044; R₂ = 0.0515. The molecular symmetry of compound I is approximately C_2ν and the axis of the two sulfur atoms lies in the same plane which includes the two phosphorus atoms and the two PC bonds with the Bu^t groups. Reaction of the lithio compound Fe₂(CO)₆(Bu^tPLi)₂ with CH₂I₂ yielded Fe₂(CO)₆(Bu^tP)₂CH₂, along with an iron cluster of unknown structure.     

The Ylide Adduct SOC2(PPh3)2 as Complex Ligand. Reaction with [Mn2(CO)10] and InCl3; Crystal Structures of [(CO)4Mn(SOC2{PPh3}2)2][Mn(CO)5] and (H2C{PPh3}2)[InCl4]2

The betain‐like SOC₂(PPh₃)₂ ( 1a ) reacts with [Mn₂(CO)₁₀] in THF to produce the salt‐like complex [(CO)₄Mn(SOC₂{PPh₃}₂)₂][Mn(CO)₅] ( 2 ). 1a is bonded via the sulfur atoms which are arranged in trans position in the octahedral environment of the manganese atom. With InCl₃ from CH₂Cl₂ solution the addition product [Cl₃In(SOC₂{PPh₃}₂)] ( 3 ) is obtained along with the salt (H₂C{PPh₃}₂)[InCl₄]₂ ( 4 ), which is the result of proton abstraction from the solvent. The crystal structures of 2· 0.5THF and 4· CH₂Cl₂ are reported. The compounds are further characterized by IR and ³¹P NMR spectroscopy.