Neue Phosphor-verbrückte Übergangsmetallcarbonyl-Komplexe Die Kristallstrukturen von [Re2(CO)7(PtBu)3], [Co4(CO)10(PtBu)2], [Ir4(CO)6(PtBu)6] und [Ni4(CO)10(PiPr)6]

New Phosphorus-bridged Transition Metal Carbonyl Complexes. The Crystal Structures of [Re₂(CO)₇(P^tBu)₃], [Co₄(CO)₁₀(P^tBu)₂], [Ir₄(CO)₆(P^tBu)₆], and [Ni₄(CO)₁₀(PⁱPr)₆], (P^tBu)₃ reacts with [Mn₂(CO)₁₀], [Re₂(CO)₁₀], [Co₂(CO)₈] and [Ir₄(CO)₁₂] to form the multinuclear complexes [M₂(CO)₇(P^tBu)₃] (M = Re ( 1 ), Mn ( 5 )), [Co₄(CO)₁₀(P^tBu)₂] ( 2 ) and [Ir₄(CO)₆(P^tBu)₆] ( 3 ). The reaction of (PⁱPr)₃ with [Ni(CO)₄] leads to the tetranuclear cluster [Ni₄(CO)₁₀(PⁱPr)₆] ( 4 ). The complex structures were obtained by X-ray single crystal structure analysis: ( 1 : space group P1 (Nr. 2), Z = 2, a = 917.8(3) pm, b = 926.4(3) pm, c = 1 705.6(7) pm, α = 79.75(3)°, β = 85.21(3)°, γ = 66.33(2)°; 2 : space group C2/c (Nr. 15), Z = 4, a = 1 347.7(6) pm, b = 1 032.0(3) pm, c = 1 935.6(8) pm, β = 105.67(2)°; 3 : space group P1 (Nr. 2), Z = 4, a = 1 096.7(4)pm, b = 1 889.8(10)pm, c = 2 485.1(12) pm, α = 75.79(3)°, β = 84.29(3)°, γ = 74.96(3)°; 4 : space group P2₁/c (Nr. 14), Z = 4, a = 2 002.8(5) pm, b = 1 137.2(8) pm, c = 1 872.5(5) pm, β = 95.52(2)°).     

(μ-FcC≡CH)Co2(CO)6簇合物羰基取代衍生物的合成和分子结构

The substituted reactions of (μ-FcC≡CH)Co₂(CO)₆ with PPh₃, AsPh₃ and dppm have been studied and three new substituted derivatives have been obtained. The compounds were characterized by elemental analysis, IR, ¹H NMR, MS and X-ray crystallography. They have the following formula: (μ-FcC≡CH)Co₂(CO)_6-nL[n=1, L=PPh₃（2）, AsPh₃（3）; n=2, L=dppm (4)]. The cluster 2 crystallizes in monoclinic, space group P2₁/n, with a=1.342 4(8) nm, b=1.305 4(8) nm, c=1.875 0(9) nm, β=103.084(9)°, V=3.201(3) nm³, Z=4, F(000)=1 480, D_c=1.515 g·cm^-3, μ=15.62 cm^-1; final R indices [I > 2σ(I)]: R₁=0.040 9, ωR₂=0.076 9; S=1.007, Δρ_max=463e·nm^-3, Δρ_min=-395 e·nm^-3. The cluster 3 crystallizes in monoclinic, space group P2₁/n, with a=1.341 0(4) nm, b=1.307 9(4) nm, c=1.912 0(5) nm, β=103.043(5)°, V=3.267(15) nm³, Z=4, F(000)=1 552, D_c=1.574 g·cm^-3, μ=24.87 cm^-1; final R indices[I> 2σ（I）]：R₁=0.0437, ωR₂=0.078 2; S=0.995, Δρ_max=530 e·nm^-3, Δρ_min=-444 e·nm^-3. CCDC: 221860, 2; 221863, 3.     

Synthese und Struktur der Phosphor-verbrückten Übergangsmetallkomplexe [Fe2(CO)6(PR)6] (R = tBu,iPr), [Fe2(CO)4(PiPr)6], [Fe2(CO)3Cl2(PtBu)5], [Co4(CO)10(PiPr)3], [Ni5(CO)10(PiPr)6] und [Ir4(C8H12)4Cl2(PPh)4]

Synthesis and Structure of the Phosphorus-bridged Transition Metal Complexes [Fe₂(CO)₆(PR)₆] (R = ^tBu, ⁱPr), [Fe₂(CO)₄(PⁱPr)₆], [Fe₂(CO)₃Cl₂(P^tBu)₅], [Co₄(CO)₁₀(PⁱPr)₃], [Ni₅(CO)₁₀(PⁱPr)₆], and [Ir₄(C₈H₁₂)₄Cl₂(PPh)₄] (P^tBu)₃ and (PⁱPr)₃ react with [Fe₂(CO)₉] to form the dinuclear complexes [Fe₂(CO)₆(PR)₆] (R = ^tBu: 1 ; ⁱPr: 2 ). 2 is also formed besides [Fe₂(CO)₄(PⁱPr)₆] ( 3 ) in the reaction of [Fe(CO)₅] with (PⁱPr)₃. When PⁱPr(P^tBu)₂ and PⁱPrCl₂ are allowed to react with [Fe₂(CO)₉] it is possible to isolate [Fe₂(CO)₃Cl₂(P^tBu)₅] ( 4 ). The reactions of (PⁱPr)₃ with [Co₂(CO)₈] and [Ni(CO)₄] lead to the tetra- and pentanuclear clusters [Co₄(CO)₁₀(PⁱPr)₃] ( 5 ), [Ni₄(CO)₁₀(PⁱPr)₆] [2] and [Ni₅(CO)₁₀(PⁱPr)₆] ( 6 ). Finally the reaction of [Ir(C₈H₁₂)Cl]₂ with K₂(PPh)₄ leads to the complex [Ir₄(C₈H₁₂)₄Cl₂(PPh)₄] ( 7 ). The structures of 1–7 were obtained by X-ray single crystal structure analysis (1: space group P2₁/c (Nr. 14), Z = 8, a = 1 758.8(16) pm, b = 3 625.6(18) pm, c = 1 202.7(7) pm, β = 90.07(3)°; 2 : space group P1 (Nr. 2), Z = 1, a = 880.0(2) pm, b = 932.3(3) pm, c = 1 073.7(2) pm, α = 79.07(2)°, β = 86.93(2)°, γ = 72.23(2)°; 3 : space group Pbca (Nr. 61), Z = 8, a = 952.6(8) pm, b = 1 787.6(12) pm, c = 3 697.2(30) pm; 4 : space group P2₁/n (Nr. 14), Z = 4, a = 968.0(4) pm, b = 3 362.5(15) pm, c = 1 051.6(3) pm, β = 109.71(2)°; 5 : space group P2₁/n (Nr. 14), Z = 4, a = 1 040.7(5) pm, b = 1 686.0(5) pm, c = 1 567.7(9) pm, β = 93.88(4)°; 6 : space group Pbca (Nr. 61), Z = 8, a = 1 904.1(8) pm, b = 1 959.9(8) pm, c = 2 309.7(9) pm. 7 : space group P1 (Nr. 2), Z = 2, a = 1 374.4(7) pm, b = 1 476.0(8) pm, c = 1 653.2(9) pm, α = 83.87(4)°, β = 88.76(4)°, γ = 88.28(4)°).     

Über die Reaktionen von CH2=P(NMe2)3 mit Fe(CO)5, Cr(CO)6 und CS2; Molekülstrukturen von [MeP(NMe2)3][(CO)5CrC(O)CH=P(NMe2)3] und (CO)4Fe=C(OMe)CH=P(NMe2)3

The Reactions of CH₂=P(NMe₂)₃ with Fe(CO)₅, Cr(CO)₆, and CS₂; Molecular Structures of [MeP(NMe₂)₃][(CO)₅CrC(O)CH=P(NMe₂)₃], and (CO)₄Fe=C(OMe)CH=P(NMe₂)₃ The ylide CH₂=P(NMe₂)₃ ( 1 ) reacts with several binary transition metal carbonyls M(CO)_x to produce the corresponding salt like compounds [MeP(NMe₂)₃][(CO)_x–1MC(O)CH=P(NMe₂)₃] (M = Fe ( 3 ), Cr ( 4 )). The related reaction with CS₂ leads to the salt [MeP(NMe₂)₃][SC(S)CH=P(NMe₂)₃] ( 2 ). While 4 is thermally stable, 3 rapidly decomposes at room temperature with formation of [MeP(NMe₂)₃]₂[Fe₂(CO)₈] ( 8 ). Alkylation of 3 (at –50 °C) and 4 with MeSO₃CF₃ produces the related carbene complexes (CO)_x–1M=C(OMe)CH=P(NMe₂)₃ ( 5 ) and ( 6 ); the reaction of 3 with Me₃SiCl results in the formation of the carbene complex (CO)₄Fe=C(OSiMe₃)CH=P(NMe₂)₃ ( 7 ). 4 crystallizes in the space group P2₁2₁2₁ (No. 19) with a = 1111.1(2), b = 1476.1(3), c = 1823.1(4) pm and Z = 4. 5 crystallizes in the space group P2₁/n (No. 14) with a = 1303.6(3), b = 910.5(4), c = 1627.0(4) pm, β = 96.06(2)° and Z = 4. The compounds have been characterized by elemental analyses, NMR (¹H, ¹³C, ³¹P) and IR spectroscopy.     

大基团取代不对称茂钛（Ⅳ）化合物的合成

大基团取代不对称茂钛（Ⅳ）化合物的合成舒学军贺峥杰＊陈寿山（南开大学元素有机化学研究所天津３０００７１）关键词有机锂，富烯，茂钛化合物，合成１９９６－０６－１９收稿，１９９６－１２－３１修回国家自然科学基金资助课题取代茂钛化合物常常是烯烃异构化的良好...     

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.     

Synthesis and Crystal Structure of (CO)5ReSnMe2Re(CO)5

１ＩＮＴＲＯＤＵＣＴＩＯＮＨｏｍｏ ｄｉｎｕｃｌｅａｒｍｅｔａｌｃａｒｂｏｎｙｌｃｌｕｓｔｅｒｓｈａｖｅｂｅｎｓｔｕｄｉｅｄｗｉｄｅｌｙｆｏｒｔｈｅｉｒｎｏｖｅｌｓｔｒｕｃｔｕｒｅｓａｎｄｕｓｅｓｉｎｏｒｇａｎｉｃｓｙｎｔｈｅｓｉｓ〔１〕．Ｅｘａｍｐ...     

Synthesis and characteristics of novel pentanuclear complexes [(OC)3Mn(η1,η5-C5H4)Fe(CO)2(η1,η5-C5H4CO2)]2M(η5-C5H5)2 (M=Ti, Zr)

The reaction of Cp₂MCl₂ complexes (M=Ti and Zr) with 2 equiv. of (OC)₃Mn(η¹,η⁵-C₅H₄)Fe(CO)₂(η⁵-C₅H₄COONa) results in the formation of the pentanuclear complexes (OC)₃Mn(η¹,η⁵-C₅H₄)Fe(CO)₂(η⁵-C₅H₄CO₂)]₂M(η⁵-C₅H₅)₂, which are characterized by IR and¹H NMR spectroscopy and cyclic voltammetry. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1055–1058, May, 1997.     

Synthesis and Structure Characterization of Mn2（CO）6（μ—S2CP^iPr3）

1INTRODUCTIONThechemistryofhomobinuclearcomplexeshasbeenaveryactivefieldofresearchinthepastdecadesbecauseoftheirnovelstructuresandapplicationsinorganicsynthesis[1,2].Atthesametimephosphine-carbondisulfideadducts,S2CPR3,areveryversatileligandswithavarietyofcoo-rdinationmodestotransitionmetalcenters.Itisabletoformallydonatefrom2to8etoametalormetals[3].AlthoughMn2(CO)6(m-S2CPiPr3)hasbeensynthesizedbyMiguelD.etal.[4,5],nocrystallo-graphicdatatillnowareavailableforit.Inthispaperwewilldesc…     

Synthese und Struktur von (Ph3PAu)3Mn(CO)4

Synthesis and Structure of (Ph₃PAu)₃Mn(CO)₄ Photolysis of (Ph₃PAu)Mn(CO)₅, Ph₃PAuN₃ and Ph₃PAuNCO yields (Ph₃PAu)₃Mn(CO)₄ ( 1 ). 1 crystallizes in the monoclinic space group P2₁/n with a = 1 031.3(1); b = 3 095.2(3), c = 3 386.3(3) pm; β = 97.58(3)°; Z = 8. The crystal structure contains two symmetry independent clusters 1 of the same geometry. Their inner core MnAu₃ forms a rhombus with distances Mn? Au of about the same lengths between 258.4(4) and 262.0(4) pm. The distances Au? Au range from 276.6(2) to 281.3(2) pm. The bonding in 1 is discussed and compared with those of (Ph₃PAu)₃Co(CO)₃ having the same total number of electrons but a tetrahedral framework.     

Synthese und Struktur von [(Ph3PAu)6Co(CO)2](PF6) und [(Ph3PAu)7Co(CO)2](PF6)2

Synthesis and Structure of [(Ph₃PAu)₆Co(CO)₂](PF₆) and [(Ph₃PAu)₇Co(CO)₂](PF₆)₂ By the reaction of (Ph₃PAu)₄Co[(CO)₃]⁺ with OH^? in the presence of excess Ph₃PAuCl the larger cluster cations [(Ph₃PAu)₆Co(CO)₂]⁺ ( 1 ) and [(Ph₃PAu)₇Co(CO)₂]²⁺ ( 2 ) can be built up with 1 being the main product. 1 crystallizes with PF^?₆ as counterion in the monoclinic space group C2/c with a = 3008.3(6); b = 1339.1(2); c = 2909.4(6) pm; β = 103.08(1)°; Z = 4. The inner core of the cluster cation 1 with the symmetry C₂ has the form of a bicapped trigonal bipyramid with the heteroatom in equatorial position, and distances Au? Au between 280.4(1) and 288.4(1) pm and Co? Au between 254.9(1) and 257.1(2) pm. 2 · (PF₆)₂ crystallizes in the triclinic space group P1 with a = 2155.7(1); b = 1720.6(1); c = 3543.6(1) pm; α = 91.89(1)°; β = 97.51(1); γ = 89.92(1)°; Z = 4. The unit cell contains two symmetry independent cluster cations 2 of about the same geometry. The cluster skeleton Au₇Co can be described as fragment of an icosahedron formed by seven gold atoms with the Co atom in its center. The Au? Au distances range from 274.8(3) to 332.6(3) pm, and the Co? Au distances are 256.8(6) to 264.7(5) pm. The bonding in 1 and 2 is discussed.     

Organometallic Compounds of the Lanthanides. 127 [1] Synthesis of Monomeric Bis(cyclopentadienyl)lanthanide Tetrahydroborates with Bulky Cyclopentadienyl Ligands. Single Crystal X-ray Structures of [(η5-C5Me5)2SmBH4(THF)] and [(η5-C5Me4Et)2Y(μ-H)2BH2(THF)]

The trichlorides of yttrium, samarium, and lutetium react with 2 equivalents of Na[C₅H₄ ^tBu] and 1 equivalent of NaBH₄ to give [(η⁵-C₅H₄ ^tBu)₂LnBH₄(THF)] (Ln = Y ( 1 ), Sm ( 2 ), Lu ( 3 )) or with 2 equivalents of Na[C₅Me₄R] and 1 equivalent of NaBH₄ to form [(η⁵-C₅Me₄R)₂ · LnBH₄(THF)] (R = H, Ln = Y ( 4 ), Sm ( 5 ), Lu ( 6 ); R = Me, Ln = Y ( 7 ), Sm ( 8 ), Lu ( 9 ); R = Et, Ln = Y ( 10 ), Sm ( 11 ), Lu ( 12 ); R = ⁱPr, Ln = Y ( 13 ), Sm ( 14 ), Lu ( 15 )). The new compounds have been characterized by elemental analysis, NMR spectroscopy and mass spectrometry. The crystal structures of 8 and 10 were determined by single crystal X-ray diffraction.     

Ge4Br4[Mn(CO)5]4 and Ge6Br2[Mn(CO)5]6: first germanium cluster compounds containing Mn(CO)5 ligands

Cluster compounds of germanium exhibiting germanium-germanium bonds, where the germanium atoms are additionally bound to transition metal ligands, are rare. Here a synthetic pathway to such cluster compounds is described, starting from metastable Ge I halide solutions leading to the two cluster compounds Ge4Br4[Mn(CO)5]4 and Ge6Br2[Mn(CO)5]6, being the first examples of germanium cluster compounds bearing Mn(CO)5 ligands. The Ge6 compound exhibits a novel arrangement of germanium atoms that has not been previously observed in ligand stabilized cluster compounds of germanium, neither with organic nor with transition metal ligands. The bonding situation inside the cluster compounds is discussed, together with a possible reaction pathway that opens the way to metalloid cluster compounds of germanium exhibiting Mn(CO)5 ligands.     

Hydrothermal Synthesis and Crystal Structure of Complex Mn2(phen)2(p-MBA)4(H2O)

A novel Mn(Ⅱ)complex Mn2(phen)2(p-MBA)4(H2O)has been hydrothermally synthesized by the reaction of P-methyl benzoic acid(p-MBA)with 1,10-phenanthroline(phen).Crystal data for this complex:monoclinic,space group C2/c,a=2.3328(3),b=1.5549(2),c=1.5557(2)nm,β=121.726(2)°,V=4.7997(11)nm3,Mr=1028.85,Dc=1.424 g/cm3,Z=4,F(000)=2128,μ(MoKa)=0.590mm-1,GOOF=1.060,R=0.0333 and wR=0.0767.In the crystal,each Mn(Ⅱ)ion is coordinated by two nitrogen atoms from one o-phenanthroline molecule.three oxygen atoms from three P-methyl benzoic acids and one oxygen atom from one water molecule,giving a six-coordinate distorted octahedral coordination geometry.Two neighboring Mn(Ⅱ)ions are bridged by two P-methyl benzoic acid groups and one water molecule,and their end positions are respectively coordinated by one 1,10-phenanthroline and one p-methyl benzoic acid molecule,giving a binuclear cage structure,of which the Mn(Ⅱ)…Mn(Ⅱ)distance is 0.3502 nm.     

Syntheses and Characterizations of （η~5－C_5H_5）MoFeCo（CO）_8（μ_3－S） and （η~5－C_5H_5）_2Mo_2Fe（CO）_7（μ_3－S）：X－ray Crystal Structure of （η~5－C_5H_5）MoFeCo（CO）_8（μ_3－S）

ＳｙｎｔｈｅｓｅｓａｎｄＣｈａｒａｃｔｅｒｉｚａｔｉｏｎｓｏｆ（η~５－Ｃ_５Ｈ_５）ＭｏＦｅＣｏ（ＣＯ）_８（μ_３－Ｓ）ａｎｄ（η~５－Ｃ_５Ｈ_５）_２Ｍｏ_２Ｆｅ（ＣＯ）_７（μ_３－Ｓ）：Ｘ－ｒａｙＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ（η~５－Ｃ_５Ｈ_...     

Formation of the Salt‐like Complexes [Co{S2CC(PPh3)2}3][Co(CO)4]3 and [(CO)4Mn{S2CC(PPh3)2}][Mn(CO)5] from the Reaction of the Related Carbonyl Compounds with S2CC(PPh3)2

The betain‐like compound S₂CC(PPh₃)₂ ( 1 ), which is obtained from CS₂ and the double ylide C(PPh₃)₂, reacts with [Co₂(CO)₈] and [Mn₂(CO)₁₀] in THF to afford the salt‐like complexes [Co{S₂CC(PPh₃)₂}₃][Co(CO)₄]₃ ( 2 ) and [(CO)₄Mn{S₂CC(PPh₃)₂}][Mn(CO)₅] ( 3 ), respectively, in good yields. At both d⁶ cations 1 acts as a chelating ligand. Disproportionation reactions from formal Co⁰ into Co^III and Co^?I and from Mn⁰ into Mn^I and Mn^?I occurred with the removal of four or one carbonyl groups, respectively. The crystal structures of 2· 5.5THF and 3· 2THF are reported, which show a shortening of the C–C bond in the ligand upon complex formation. The compounds are further characterized by ³¹P NMR and IR spectroscopy.     

[(TeMe2)Mn(CO)4(μ5-Te)(μ4-Te)Mn4(CO)12]−: A Pentacoordinate Bridging Tellurido Ligand in a Square-Pyramidal Geometry

The first Te–Mn–CO clusters were obtained by the thermal reaction of K₂TeO₃ with [Mn₂(CO)₁₀] in MeOH. The basicity of the μ₄-Te ligand in the octahedral cluster anion [(μ₄-Te)₂Mn₄(CO)₁₂]²⁻ is demonstrated by its binding to the fragment [(TeMe₂)Mn(CO)₄]⁺ in an axial fashion to afford the novel cluster 1 .