John H. Yamamoto

Coordination and fragmentation of 1,4-dithiacyclohexane by a triosmium cluster☆

Abstract The reactions of 1,4-dithiacyclohexane (1,4-DTCH) with Os3(CO)10(NCMe)2, Os3(CO)11(NCMe) and Os3(CO)12 have been investigated. The reaction of 1,4-DTCH with Os3(CO)11(NCMe) at 25 °C yielded Os3(CO)11( SCH 2 CH 2 SCH 2 C H2) (1 in 46% yield. The reaction of 1,4-DTCH with Os3(CO)10(NCMe)2 at 25 °C yielded Os3(CO)10 SCH 2 CH 2 SCH 2 C H2) (2) in 75% yield. Compound 2 was characterized by a single crystal X-ray diffraction analysis. The molecule consists of a triangular triosmium cluster with ten linear terminal carbonyl ligands, and a 1,4-DTCH ligand coordinated as a chelate to only one of the metal atoms. When compound 2 was heated to reflux in cyclohexane solvent four compounds were obtained: Os 3 ( CO ) 9 (μ 3 -ν 2 - CCH 2 (μ- H ) 2 ( 3 ), Os 2 ( CO ) 6 (μ- SCH 2 CH 2 S )( 4 ), Os 3 ( CO ) 10 (μ- SCH 2 CH 2 S )( 5 ), Os 3 ( CO ) 8 (μ 3 0-ν 2 - C  CH 2 )( SCH 2 CH 2 SCH 2 C H 2 )(μ- H ) 2 ( 6 ) . The formation of ethylene as a coproduct was observed spectroscopically when the reaction was performed in toluene-d8 solvent in an NMR tube at 100 °C. The same cluster complexes were obtained from the pyrolysis of 1, and from the direct reaction of 1,4-DTCH with Os3(CO)12 at 125 °C. Compounds 4 and 5 were characterized by single crystal X-ray diffraction analysis. Both compounds contain a bridging, chelating ethanedithiolato, SCH2CH2S, ligand. Compound 4 can be obtained from 5 in good yield by heating to 125 °C in octane solvent. Compound 3 has been reported previously. Compound 6 is a simple 1,4-DTCH derivative of 3. Crystallographic data for 2: Os3S2O10C14H8, space group, P2 1 /n, a=8.641(2), b=25.108(4), c=10.533(1) A , β=113.35(1)°, Z=4,2064 reflections, R=0.037. For 4: Os2S2O6C8H4, space group P2 1 /n, a=8.612(2), b=16.062(8), c=9.988(4) A , β=98.37(1)°, Z=4, 1295 reflections, R=0.044. For 5 Os3S2O10C12H4, space group P2 1 /c, a=14.079(2), b=9.383(1), c=15.153(2) A , β=108.20(8)°, Z=4 , 1893 reflections, R=0.030.

Bis-ethanedithiolate triruthenium cluster complexes from the reaction of Ru3(CO)12 with 1,2,5, 6-tetrathiacyclooctane

The reaction of 1,2,5,6-tetrathiacyclooctane with Ru3(CO)12 in methylene chloride solvent at 40°C has yielded two new isomericbis-thane-1,2-dithiolate triruthenium carbonyl cluster complexes:anti-Ru3(CO)7(μ-SCH2CH2S)2, 1 andsyn-Ru3(CO)7(μ-SCH2CH2S)2,2, and the previously reported diruthenium compound, Ru2(CO)6(μ-SCH2CH2S).3 in 24 %, 5 %, and 26 % yields, respectively. Compounds1 and2 were characterized by a single crystal X-ray diflraction analyses. Both compounds consist of a open triangular triruthenium clusters with seven terminal carbonyl ligands and a bridging ethanedithiolate ligand across each of the metal metal bonds in the complex. When heated to 60° C, compound1 was trans[formed into a mixture of2 and3. Crystallographic data for1: Ru3S4O7C11H8, space group, P21/a,a= ll.830(2)A,b= 10.576(1)A,c= 16.012(1)A,β= 100.53(2)°,Z=4, 1808 reflections,R= 0.029. For2: Ru3 S4O7C11H8, space group P1,a= 9.945(l)A,b= 11.323(1)A.c= 9,788(1)A,a= 108.73(1)°,β= 104,67(1)°,y= 103.59(2)°,Z = 2, 2046 rellections.R = 0.021.

Oxide bridged mixed metal organometallics: the reaction of Ru4(CO)13[μ3-PN(R)2] R=iPr, Cy with Cp*W(O)2CCPh

Abstract The reaction of the tungsten oxo acetylide complex Cp*W(O)2CCPh with Ru4(CO)12–13[μ3-PN(R)2] where R=iPr or Cy affords two oxo bridged metal clusters η5-Cp*W(μ-O)Ru4(CO)9(μ-CO)[μ3-η2-P(O)N(R)2](μ4-η2-CCPh) (2) and η5-Cp*W(μ-O)2Ru4(CO)10[μ3-PN(R)2](μ4-η2-CCPh) (3). X-ray analysis shows that 2 has a single W–O–Ru oxide bridge and contains the first example of a diisopropylaminophosphinidoxo ligand while in 3 both oxide ligands bridge W–Ru bonds. The reaction of 3 with HBF4 · Et2O forms the new W–F complex η5-Cp*WF(μ3-O)HRu4(CO)9[μ3-η2-P(O)N(R)2](μ4-η2-CCPh) (4).

Precursors of quadruply bridging phosphorus monoxide ligands: synthesis and structural characterization of a new family of anionic fluoro and alkoxyphosphinidene clusters Ru5(CO)15(μ4-PR) (R = NiPr2, NCy2, F, OMe, OEt, OiPr): generation and structure of [H2NCy2][Ru5(CO)15(μ4-PO)]

A new family of phosphorus functionalized, pentanuclear ruthenium clusters Ru5(CO)15(μ4-PR) [R = NiPr2, NCy2, F, OMe, OEt, OiPr, O−] has been synthesized and representative compounds structurally characterized. The reaction of Ru4(CO)13(μ3-PNR2) (1) (R = Cy, iPr) with Ru3(CO)12 in refluxing heptane yields H2Ru3(CO)9(μ3-PNR2) (2) and Ru5(CO)15(μ4-PNR2) (3). An alternative high-yield synthesis for 3 is the reaction of 1 with Ru(CO)5 in refluxing hexane. Treatment of 3 with HBF4·Et2O produces Ru5(CO)15(μ4-PF) (4) in high yield. In contrast, refluxing 3 with HBF4·H2O in CH2Cl2 yields 4 and [R2NH2][Ru5(CO)15(μ4-PO)] (5), a cluster containing a μ4-phosphorus monoxide (PO) ligand. The reaction of 4 with alcohols affords the series of alkoxy phosphinidene cluster complexes Ru5(CO)15(μ4-POR′) (6) (R′ = Me, Et, iPR). The structures of 2a (R = NCy2), 3a (R = NCy2), 4 (R = F), and the phosphorus monoxide cluster [H2NCy2][Ru5(CO)15(μ4-PO)] (5a and 6a) (R′ = Me) have been determined by X-ray diffraction studies.

Synthesis and structure of a series of tungsten(II) and tungsten(VI) diynyl and diyndiyl complexes

Oxidation of the diynyl and diyndiyl complexes [W(CCCCH)(CO)3Cp*] (1) and [{W(CO)3Cp*}2(μ-CCCC)] (2) affords the corresponding dioxo compounds [W(CCCCH)(O)2Cp*] (4) and [{W(O)2Cp*}2(μ-CCCC)] (6) via oxo–peroxo intermediates. The molecular structures are consistent with a degree of mixing between the carbon orbitals of the C4(H) fragment and the d4, but not the d0, metal centres. A simple synthesis of the useful reagent WCl(CO)3Cp* is also described.

The synthesis and structural analysis of the new high nuclearity platinum-ruthenium cluster complex Pt2Ru8(CO)18(μ3−EtC2Et)2(μ4−EtC2Et) containing three alkyne ligands

AbstarctThe ten metal cluster complex Pt2Ru8(CO)23(µ3−H)2, 1 was found to react with EtC2Et to form a new ten metal tris-alkyne complex Pt2Ru8(CO)18(µ3−EtC2Et)2 (µ4−EtC2Et),2 in 35% yield. Complex 2 was characterized by IR,1H NMR , and single crystalx-ray diffraction analyses. The cluster can be viewed as a dodecahedron of eight metal atoms capped with two ruthenium carbonyl groups, two triply bridging EtC2Et ligands and one quadruply bridging EtC2Et ligand. Application of the standard electron counting procedures indicate that this is an unusual complex in which the 18 electron rule applies and the polyhedral skeletal electron pair theory does not. Crystal Data for 2 2.0.5 CH2CI2: space group = P21,a = 12.759(2) A,b=18.438(2)Å,c = 20.197(3) Å,β = 91.59(1)°, Z. = 4, 6394 reflections,R = 0.037.

Phosphorus monoxide as a quadruply bridging ligand: syntheses and X-ray crystal structures of Ru5(CO)15(µ4-PF) and [H2NCy2][Ru5(CO)15(µ4-PO)]

The reaction of Ru4(CO)13(µ3-PNCy2) 1 with Ru(CO)5 in refluxing hexane yields Ru5(CO)15(µ4-PNCy2) 2 in high yield; treatment of 2 with HBF4·Et2O forms Ru5(CO)15(µ4-PF) 3 which is the first cluster complex to contain a µ4-fluorophosphinidene ligand, while refluxing 2 with HBF4·H2O in CH2Cl2 yields 3 and the title compound [Ru5(CO)15(µ4-PO)][H2NCy2] 4, an unprecedented example of a cluster complex containing a µ4-PO ligand.