Synthesis and Structure of a Dimolybdenum Carbonyl Compound with Thiolato-Bridges [Et4N] 2 [Mo2 (CO) 8 (SC6H4-Cl -p) 2]

Reaction of Mo (CO)6 with p-Cl-C6H4SNa and Et4NCl · H2O in CH3CN afforded a dinuclear molybdenum (0) compound [Et4N]2 [Mo2 (CO)8 (SC6H4-Cl-p)2] (1). The crystal structure was determined by X-ray diffraction. The crystallographic data: C36H48Cl2Mo2N2O8S2, Mr= 963.71, monoclinie, P21/c, a=9. 269(4),b=13.750(3), c=17.466(6) A ;β=104.84(3)°; V=2151.8(3) A3; Z=2; Dc=1.49 g/cm3; F(000)=984; μ=8.3 cm-1; MoKα radiation (λ=0. 71073A ); Final R = 0. 055 and Rw=0. 065 for 3287 reflections with I＞3. 0σ(I). The X-ray structure analysis revealed that the Mo2S2 core is planar. The geometry around each Mo atom is a distance is 4. 014(2) A , and this obviously indicates the absence of Mo-Mo bond.     

Synthesis and Structure of Dinuclear Molybdenum Carbonyl Thiolate Compound[Et4N]2[Mo2(CO)8(SC6H4-CH3-p)2]

1　ＩＮＴＲＯＤＵＣＴＩＯＮＳｉｎｃｅｔｈｉｏｌａｔｅｌｉｇａｎｄｗａｓｉｎｔｒｏｄｕｃｅｄｉｎｔｏｍｏｌｙｂｄｅｎｕｍｃａｒｂｏｎｙｌｃｏｍｐｏｕｎｄｉｎ1 984 [1],ｔｈｅｉｎｖｅｓｔｉｇａｔｉｏｎｏｎｌｏｗ ｖａｌｅｎｃｅＭｏ -ＳＲｃｏｍｐｏｕｎｄｓｈａｓｒｅｃｅｉｖｅｄａｔｔｅｎｔｉｏｎｆｏｒｔｈｉｓｋｉｎｄｏｆｌｏｗ ｖａｌｅｎｃｅｃｏｍｐｏｕｎｄｓｐｏｓｓｅｓｓｃｅｒｔａｉｎａｄｖａｎｔａｇｅｏｎｃｏｍｐｏｕｎｄｓｙｎ ｔｈｅｓｉｓ,ｍｏｌｅｃｕｌｅｓｔｒｕｃｔｕｒｅａｎｄｐｈｙｓｉｃａｌａ…     

Synthesis and Structure of Dimolybdenum Carbonyl Thiolate Compound [Et4N]2[Mo2（CO）8（SC6H4—CH3—m）2]

1 INTRODUCTION In 1984, thiolate ligand was successfully introduced into molybdenum carbonyl compound by the reaction of Mo(CO)6 with [Et4N]SR( R = C6H5, But) in a moderate condition[1]. From then on, a series of dinuclear molybdenum(0) carbonyl thiolate compounds have been synthesized and characterized by using a variety of thiolate ligands in our research group. It was found that a planar Mo2S2 unit is in the compound [Et4N]2[Mo2(CO)8(SC6H4-CH_3-p)2][2] (2) and a "butterfly" t…     

Synthesis and Structure of Dinuclear Molybdenum Carbonyl Thiolate Compound〔Et_4N〕_2〔Mo_2(CO)_8(SC_6H_4-NH_2-p)_2〕

１ＩＮＴＲＯＤＵＣＴＩＯＮＴｈｅｅｘｉｓｔｅｎｃｅａｎｄｓｉｇｎｉｆｉｃａｎｃｅｏｆｔｈｅｍｏｌｙｂｄｅｎｕｍ ｓｕｌｆｕｒｂｏｎｄｉｎｇｉｎｍｏｌｙｂｄｅｎｕｍｅｎｚｙｍｅｓ〔１〕ｈａｖｅｓｔｉｍｕｌａｔｅｄｔｈｅｓｔｕｄｉｅｓｏｎｔｈｅｃｈｅｍｉ...     

Reaction of Mo(CO)_6 with Alkoxide: Synthesis and Structure of the Mo(0)-OR Complex [Et_4N]_3[Mo_2(CO)_6(μ-OC_6H_4OCH_2C_6H_5)_3]

The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo(0) compound [Et4N]3[Mo2(CO)6(μ-OC6H4OCH2- C6H5)3] 1. 1 crystallizes in monoclinic, space group P21/c with a = 15.359(2), b = 18.378(3), c = 24.952(2), β = 102.268(4)°, V = 6882.3(16) 3, Mr = 1348.34, Z = 4, Dc = 1.301 g/cm3, F(000) = 2832 and μ = 0.424 mm-1. The final R = 0.0606 and wR = 0.1552 for 9396 observed reflections (I > 2σ(I)). 1 contains a [Mo2O3]3- core in triangular bi-pyramidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three μ-O atoms from C6H5CH2OC6H4O- bridging ligands. The Mo…Mo distance is 3.30(8) , indicating no metal- metal bonding. A formation pathway via forming a di-molybdenum(0) di-bridging OR compound [Mo2(μ-OR)2(CO)8]2- has been figured out and the reaction of Mo(CO)6 with alkoxide has also been discussed.     

Synthesis and Structure of a New Dinuclear Molybdenum(I) Compound with Cyclohexanthiolate Ligand, [Mo_2(SC_6H_(11))_2(CO)_6(CH_3CN)_2]

1 INTRODUCTION The chemistry of complexes containing low-valence molybdenum and tungsten metal atoms hasincreasingly attracted the attention from chemistsand bioinorganic chemists due to their significancefor studying metal enzymes[1～5]. Since the s…     

Reaction of Mo(CO)6 with Alkoxide: Synthesis and Structure of the Mo(0)-OR Complex [Et4N]3[Mo2(CO)6(μ-OC6H4OCH2C6H5)3]

The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo(0) compound [Et4N]3[Mo2(CO)6(μ-OC6H4OCH2- C6H5)3] 1. 1 crystallizes in monoclinic, space group P21/c with a=15.359(2), b=18.378(3), c=24.952(2)(A), β=102.268(4)°, V=6882.3(16) (A)3, Mr=1348.34, Z=4, Dc=1.301 g/cm3, F(000)=2832 and μ= 0.424 mm-1. The final R=0.0606 and wR=0.1552 for 9396 observed reflections (Ⅰ ＞ 2σ(Ⅰ)). 1 contains a [Mo2O3]3- core in triangular bi-pyramidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three μ-O atoms from C6H5CH2OC6H4O- bridging ligands. The Mo…Mo distance is 3.30(8) (A), indicating no metalmetal bonding. A formation pathway via forming a di-molybdenum(0) di-bridging OR compound [Mo2(μ-OR)2(CO)8]2- has been figured out and the reaction of Mo(CO)6 with alkoxide has also been discussed.     

Synthesis and Structure of Tungsten Carbonyl Compound with 2-Mercapto Pyrimidine [Et_4N] [W (CO)_4(SC_4H_3,N_2) ]

1INTR0DUCTI0NLowva1encemolybdenum/tungstencomp1exeswiththiolatoligandsareusefulforthestudiesonsyntheticandstructuralchemistry.Inrecentyearswehavesynthe-sizedandcharacterizedaseriesofdinuclearMo-SRc0mpoundscontainingaplanarMoSzMocorewithamon0dentatethiolatoligand"-"anda"butterfly"M0S2Mocorewithabidentatethi0latoligand"=."H0wdoesmultidentateliganddo"hasnaturallyattracted0urinterest-2-mercaptoPyrimidine(PymS)wasusedasamultidentateligandtocarry0utsynthesisexperiment.unexpectedly,whichgavea…     

Synthesis and Crystal Structure of a Molybdenum Carbonyl Compound with Thiolate and Dithiocarbamate Ligands,[Bu4N][(OC)4Mo(μ-SC6H5)2Mo(C5H10CNS2)(CO)2]

A di-molybdenum carbonyl compound containing thiolate and dithiocarbamate li- gands, [Bu4N][(CO)4Mo(μ-SC6H5)2Mo(C5H10dtc)(CO)2] 1 (C5H10dtc = S2CNC5H10), has been pre- pared by reaction of [Mo2(SC6H5)2(CO)8] with C5H10dtcNa and [NBu4]Br in acetone. It crystallizes in monoclinic, space group P21/n with a = 13.162(3), b = 17.466(2), c = 20.453(4)(A),β = 100.77(1)°, Z = 4, V = 4619(2)(A)3, C40H56Mo2N2O6S4, Mr = 980.95, Dc = 1.389 g/cm3, μ= 7.66 cm-1, F(000) = 1988 and R = 0.0746 for 5161 observed reflections with I > 2σ(I). The complex contains a [Mo2S2]2- planar core in which one Mo atom is chelated by a C5H10dtc ligand, leading to different coordination environments of the two Mo atoms. 95Mo NMR measurement indicates that the two Mo atoms are in different oxidation states.     

CRYSTAL STRUCTURES OF [Bu4N]2[M2Ag3（ μ3—S）2（μ—S）4S2Et2dtc]（M=W,Mo）

<正> The title compounds were prepared from the reation of (NH4)2MS4 (M=W,Mo),AgNO3,NadtcEt2 and Et4NBr in CH3CN-H2O solution. The isomorphous compounds [Bu4N]2[W2Ag3S8Et2du] ( I ) and [Bu4N]2[Mo2Ag3S8Et2dtc] (Ⅱ) crystallize in triclinic space qroup Pi with the following crystal parameters:α=13. 043(4),b = 21. 640(6),c=10. 757(6)A ,α=95. 09(5),β = 91. 90(4),γ = 98. 57(3)°,Z = 2,V = 2987A3,Dc=1. 76g/cm3 for I 5;a= 12. 989(2) ,b=21. 574 (9) ,c= 10. 7/1(1) A .α= 95. 06(7), β=91. 61(4), γ=98. 52(2)°, Z = 2,V = 2961 A3.Dc= 1. 58g/cm3 for Ⅱ . The final R and Rw values are 0. 061 and 0. 072 for Ⅰ ,and 0. 062 and 0. 076 for Ⅱ The M2Ag3 (M = W, Mo) unit in anion M2Ag3S8Et2dtc forms a five-membered ring.     

STRUCTURE STUDIES OF [Et_4N]_4[Cu_8(i-mnt)_6] (i-mnt=S_2C=C(CN)_2) AND [Me_4N]_4[Cu_5Ag_3(i-mnt)_6]·H_2O

<正> [Me4N]6[Ag6(i-mnt)6].H2O(1),[Et4N]4[Cu8(i-mnt)6](2) and [Me4N]4-[Cu5Ag3(i-mnt)6].H2O(3)(i-mnt=S2C=C(CN)2) were synthesized. The crystal and molecular structure of the complex 1 was reported by us.The structure of the complex 2 was determined from single crystal X-ray diffraction data. [Et4N]4[Cu8(i-mnt)s] 2, Mr=1870.46, monoclinic, P21/n, a=14.724(6), b = 17.228(3), c=15.59(1)A,β= 100.75(7)°,V=3886.3A3;Z = 2,Dc= 1.598 g/cm3. Complex 3 has been characterized by ICP elemental analyses and IR spectrum.     

REACTIVITY OF METAL(O) DITHIOCARBAMATO CARBONYL COMPLEXES [Mo(CO)_4(S_2CNEt_2)]~- (M=Mo, W): SYNTHESIS AND STRUCTURE OF A NEW MIXED-VALENCE DINUCLEAR MOLYBDENUM-SULFUR COMPLEX, [Et_4N]_2[(CO)_4MoS_2MoS_2]

<正> The reaction of [Et4N][Mo(CO)4(S2CNEt2)] with tetraethylam-monium tetrathiomolybdate affords a new mixed-valence dinuclear molybdenum complex [Et4N]2[(CO)4MoS2MoS2] (1). 1 crystallizes in the orthorhombic space group Pbom with a = 18.403(2), b = 11.963(1), c= 13. 482(1)(?) , Z = 4, V = 2986(?)3, Dc=1. 55g/cm3, Mr = 6S2. 69. R =0. 042 and Rw =0. 057 for 1975 independent reflections with I≥3σ(I), F(000) = 1416, μ =11. 2cm-1. The structure of the anion of 1 consists of an octahedron for the lowvalent Mo atom and a tetrahedron for the high-valent Mo atom sharing an S - S edge. The Mo - Mo bond distance is 2. 992 (2) (?) and the bimetallic center MoS2Mo is planar with Mo-S of 2. 517 and 2. 231 A and MoSMo angles of 78. 04° and 77. 67°. The electron delocalization between the two Mo atoms with wide separated oxidation states is also discussed.     

CRYSTAL STRUCTURE OF [Et_4N]_2[Mo_2O_2(μ-S)_2(S_2)_2]

<正> [(C2H5)4N]2[Mo2o2S2(S2)2], Mr = 676. 74, monoclinic, P21/c, a = 13.510(2), b = 14.373(2), c=14. 777(3)(?), β = 97.53(2)°, V = 2844.7(9) (?)3, Z = 4, Dc= 1. 58g/cm3, μ(MoKα) = 13.0cm-1, F(000) = 1384, R =0. 033 for 1803 observed reflections. The structure contains discrete [Mo2O2S2(S2)2]2- anions and Et4N+ cations. The two oxygen atoms bonded to the Mo atoms are in cis-form with respect to the Mo2S2 bridging unit, with an average Mo- O distance of 1. 678 (?), The Mo…Mo distance is 2. 832(1)(?).     

Synthesis and Structure of Dinuclear Molybdenum Carbonyl Thiolate Compound 〔Et_4N〕_2〔Mo_2(CO)_8(SC_6H_4-OCH_3-p)_2〕

１　ＩＮＴＲＯＤＵＣＴＩＯＮＩｎｏｕｒｅｆｆｏｒｔｓｔｏｄｅｖｅｌｏｐｔｈｅｌｏｗ－ｖａｌｅｎｃｅＭｏ－ＳＲｃｏｍｐｏｕｎｄｓ,ｗｅｈａｖｅｆｏｕｎｄａｎＭｏ（０）－ｃｏｍｐｏｕｎｄ,〔Ｍｏ２（ＳＲ）２（ＣＯ）８〕２－,ｗｈｉｃｈｉｓｏｂｔａｉｎｅｄｆｒｏｍｔｈｅｒｅａｃｔｉｏｎｏｆＭｏ（ＣＯ）６ｗｉｔｈＲＳ－ｉｎｈｉｇｈｙｉｅｌｄ,ｐｏｓｓｅｓｓｅｓａｎｉｎｔｅｒｅｓｔｉｎｇｔｗｏ－ｅｌｅｃｔｒｏｎｔｒａｎｓｆｅｒｐｒｏｐｅｒｔｙ．Ｎｕｍｅｒｏｕｓｋｉｎｄｓｏｆｄｉｎｕｃｌｅａｒｍｏｌｙｂｄｅ…     

The Molybdenum(0) Complex [Et4N]2[Mo2(CO)6(pys)2](pys=Pyridine-2-thiolato)

The title compound tetraethylammonium hexacarbonylbis(μ-pyridine-2-thiolato-S∶S) dimolybdenum [Et4N]2[Mo2(CO)6(pys)2] crystallizes in the monoclinic, space group, P21/c with a=13.217(2), b=21.648(2), c=27.193(6)(), β=82.52(2)°, V=7714.6()3, Z=8, Mr=840.77, Dc=1.45 g/cm3, μ=7.8 cm-1, R=0.038 and Rw=0.040 for 6082 reflections with I≥3σ(I). X-ray crystal structure study reveals that the asymmetric unit of the title compound is comprised of two independent formulations of the molecular formula. Each dianion has approximate C2 symmetry and the dimetallic Mo2S2 core adopts a "butterfly" conformation with a dihedral angle between the halves of 139.3(1)° for the first independent anion and 142.8(1)° for the second one. The two pyridine rings lie on the same side of the molecule in a cis arrangement and the Mo...Mo separations are 3.76(1) and 3.838(1)().     

Cluster oxalate complexes [M3(mu3-Q)(mu2-Q2)3(C2O4)3]2- and [Mo3(mu3-Q)(mu2-Q)3(C2O4)3(H2O)3]2- (M = Mo, W; Q = S, Se): mechanochemical synthesis and crystal structure

Mechanochemical reaction of cluster coordination polymers 1infinity[M3Q7Br4] (M = Mo, W; Q = S, Se) with solid K2C2O4 leads to cluster core excision with the formation of anionic complexes [M3Q7(C2O4)3]2-. Extraction of the reaction mixture with water followed by crystallization gives crystalline K2[M3Q7(C2O4)3].0.5KBr.nH2O (M = Mo, Q = S, n = 3 (1); M = Mo, Q = Se, n = 4 (2); M = W, Q = S, n = 5 (3)). Cs2[Mo3S7(C2O4)3].0.5CsCl.3.5H2O (4) and (Et4N)1.5H0.5K{[Mo3S7(C2O4)3]Br}.2H2O (5) were also prepared. Close Q...Br contacts result in the formation of ionic triples {[M3Q7(C2O4)3](2)Br}5- in 1-4 and the 1:1 adduct {[Mo3S7(C2O4)3]Br}3- in 5. Treatment of 1 or 2 with PPh(3) leads to chalcogen abstraction with the formation of [Mo3(mu3-Q)(mu2-Q)3(C2O4)3(H2O)3]2-, isolated as (Ph4P)2[Mo3(mu3-S)(mu2-S)3(C2O4)3(H2O)3].11H2O (6) and (Ph4P2[Mo3(mu3-Se)(mu2-Se)3(C2O4)3(H2O)3].8.5H2O.0.5C2H5OH (7). All compounds were characterized by X-ray structure analysis. IR, Raman, electronic, and 77Se NMR spectra are also reported. Thermal decomposition of 1-3 was studied by thermogravimetry.     

Synthesis and Crystal Structure of Cubane—typeMolybdenum Cluster ComplexMo4S4（DTP）4[μ—SOP（OEt）2]2

1 INTRODUCTION Trinuclear molybdenum complexes with Mo3(3-S)(-O)n(-S)3n (n = 0~3) cores have been extensively studied on their diversified reactions towards various organic ligands and many metals. Many derivatives with Mo3S4 core have been rationally synthesized from the cation precursor [Mo3S4(H2O)9]4+ and its neutral derivative Mo3(3-S)(-S)3(DTP)4(H2O)[1]. However, due to their structural lability, complexes with Mo3(3-S)(-O)n(-S)3n (n = 1~3) cores have been reported limitedl…     

Synthesis and Structural Characterization of a Salt{[Co(Phen)3][Mo2S2(μ-S)2(edt)2]}2·(DMSO)2·(Et2O)(Phen = 1,10-Phenanthroline,edt = Ethane-1,2-dithiolate)

Reaction of [Et4N]2[Mo2S2(μ-S)2(edt)2] with CoCl2(6H2O and Phen in MeCN followed by recrystallization in DMSO/Et2O gave rise to dark-red block crystals of {[Co(Phen)3]- [Mo2S2(μ-S)2(edt)2]}2·(DMSO)2·(Et2O) 1 (C88H86Co2Mo4N12O3S18). 1 crystallizes in the monoclinic system, space group P21/c with a = 24.631(4), b = 16.117(3), c = 24.791(4) (A), β = 92.835°, V = 9829.3(3) (A)3, Z = 4, Mr = 2438.57, Dc = 1.648 g/cm3, F(000) = 4928, μ = 12.61 cm-1, R = 0.0936 and wR = 0.1682 for 12998 observed reflections with I > 2.0σ(I). In the structure of 1, the Co atom of the [Co(Phen)3]2+ dication is octahedrally coordinated by three Phen ligands. The Mo atom of the [Mo2S2(μ-S)2(edt)2]2- dianion is coordinated by two μ-S, one terminal S and two S atoms from edt, forming a distorted square pyramidal geometry. The mean Co-N and Mo…Mo bond distances are 2.139 and 2.872 (A), respectively.     

Syntheses and Crystal Structures of Two New Iron-sulfur Carbonyl Complexes: [Fe2(SC6H4Cl)2(CO)6]·0.5(Et2O) and [Fe3(SC6H4NH2)6(CO)6]·2(MeOH)

Two new iron-sulfur carbonyl complexes, [Fe2(SC6H4Cl)2(CO)6]·0.5(Et2O) 1 and [Fe3(SC6H4NH2)6(CO)6]·2(MeOH) 2, have been prepared and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. Crystal data for 1: monoclinic, C2/c, a = 18.4439(8), b = 11.0999(5), c = 25.1830(10)(A), β = 97.0370(10)o, V = 5116.8(4)(A)3, Z = 8, C20H13Cl2Fe2O6.50S2, Mr = 604.02, Dc = 1.568 g/cm3, μ = 1.540 mm-1, F(000) = 2424, the final R = 0.0545 and wR = 0.1454 for 3443 observed reflections with I > 2σ(I); 2: monoclinic, P21/n, a = 12.350, b = 26.3050(11), c = 16.057(A),β = 97.891(3)°, V = 5166.9(2)(A)3, Z = 4, C44H44Fe3N6O8S6, Mr = 1144.76, Dc = 1.472 g/cm3, μ = 1.128 mm-1, F(000) = 2352, the final R = 0.0442 and wR = 0.1197 for 7978 observed reflections with I > 2σ(I). Complex 1 contains one iron dimer, in which two tricarbonyliron(I) fragments are bridged together by two 4-chlorophenylthiolate ligands, whereas complex 2 contains a linear tri-iron cluster, in which two terminal tricarbonyliron(II) fragments and the central Fe(II) atom are linked together by six 4-aminophenylthiolate bridging ligands.     

Synthesis and Structural Characterization of [Cu(DMF)_6][(η~5-C_5Me_5)WS_3(CuBr)_3]_2·Et_2O

1 INTRODUCTION In the last decade, we have been interested in the synthesis of [PPh4][(h5-C5Me5)MS3] (M = Mo, W)[1, 2] , Whose organometallic trisulfido anions show high reactivity towards various transition metals[3~6] . We once reported that the reaction of [PPh4][(h5-C5Me5)WS3] with CuBr in CH3CN afforded a double incomplete-cubane cluster [PPh4]2[(h5-C5Me5)WS3(CuBr)3]2[3], while the analogous reaction of [PPh4][(h5-C5Me5)WS3] with CuBr in CHCl3 gave rise to a 揻our-…