Chemistry of di- and tri-metal complexes with bridging carbene or carbyne ligands. Part 10. Synthesis of dicobalt– and dirhodium–tungsten complexes with µ3-tolylidyne groups; crystal structures of [Co2W(µ3-CC6H4Me-4)(CO)8(η-C5H5)] and [Rh2W(µ3-CC6H4Me-4)-(acac)2(µ-CO)(CO)2(η-C5H5)](acac = acetylacetonate)

Chetcuti, Michael J.; Chetcuti, Peter A.; Jeffery, John C.; Mills, Rona M.; Mitrprachachon, P.; Pickering, Susan J.; Stone, F. Gordon A.; Woodward, Peter

doi:10.1039/dt9820000699

Cited by 29 publications

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“…Thus a purple solution of 9 reacts rapidly with elemental sulfur to provide the yellow and thermally stable thiocarbamoyl complex [MoFe(μ-SCN i Pr 2 )(CO) 5 {HB(pz) 3 }] ( 10 ). Similar reactions have been described for related bimetallic hydrocarbon-based alkylidyne complexes. ,, In the present case, the addition of sulfur to one of the prochiral FeCMo faces provides a tetrahedral FeMoCS core, and the resulting chirality is manifest in the appearance of two methine heptets and four methyl doublets (δ 0.87, 1.42, 1.50, 1.59) in the 1 H NMR spectrum of 10 . The infrared spectrum of 10 includes four carbonyl absorptions (1948, 1932, 1850, and 1832 cm -1 ), and while the intensity profile is similar to that for [MoFe(μ-SCC 6 H 3 Me 2 -2,6)(CO) 5 (η-C 5 H 5 )],33a the absorptions are moved to significantly lower frequency.…”

Section: Resultssupporting

confidence: 76%

Metallathiirenes. 3.¹ Thiocarbamoyl and Alkoxythiocarbonyl Complexes of Molybdenum(II) and Tungsten(II)

2001

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Synthetic routes to thiocarbamoyl (thiocarboxamide) complexes of divalent molybdenum and tungsten are reported: The reaction of fac-[Mo(CO) 3 (NCMe) 3 ] with N,N-dimethyl thiocarbamoyl chloride (Me 2 NC(dS)Cl) at low temperature provides a thermally labile intermediate (1) presumed on the basis of subsequent transformations to be [Mo(η 2 -SCNMe 2 )-Cl(CO) 3 (NCMe)]. Reactions of 1 with K[HB(pz) 3 ] (pz ) pyrazol-1-yl), NaC 5 H 5 , bipy, or tmeda provide the complexes [Mo(η 2 -SCNMe 2 )(CO) 2 {HB(pz 4), and [Mo(η 2 -SCNMe 2 )Cl(CO) 2 (tmeda)] (5), respectively. The complex cis,cis,trans-[Mo(η 2 -SCNMe 2 )Cl(CO) 2 (PPh 3 ) 2 ] (6) results from the oxidative addition of Me 2 NC(dS)Cl to [Mo(NCMe) 2 (CO) 2 (PPh 3 ) 2 ] and is one of two isomers obtained from the reaction of 1 with PPh 3 . The complex 2 may also be obtained from reaction of (i) K[Mo(CO) 3 {HB(pz) 3 }] with Me 2 NC(dS)Cl; (ii) [Mo(CO) 3 (η 6 -C 7 H 8 )] with Me 2 NC(dS)Cl and K[HB(pz) 3 ]; and (iii) K[HB(pz) 3 ] with either 5 or 6. Sequential treatment of either [Mo(CO) 3 -Attempts to prepare a mononuclear thiocarbamoyl complex by addition of elemental sulfur or propene episulfide to the aminomethylidyne complex [Mo(tCN i Pr 2 )(CO) 2 {HB(pz) 3 }] (8) were unsuccessful; however addition of [Fe 2 (CO) 9 ] to 8 provided the thermally unstable complex [MoFe(µ-CN i Pr 2 )(CO) 5 {HB(pz) 3 }] (9), which reacts with sulfur to provide the heterobimetallic bridging thiocarbamoyl complex [MoFe(µ-SCN i Pr 2 )(CO) 5 {HB(pz) 3 }] (10). Treating fac-[W(CO) 3 (NCMe) 3 ] sequentially with Me 2 NC(dS)Cl and K[HB(pz) 3 ] provided [W(η 2 -SCNMe 2 )(CO) 2 {HB(pz) 3 }] (11); however replacing Me 2 NC(dS)Cl with ClC(dS)OC 6 H 4 -Me-4 led to [WCl(CO) 3 {HB(pz) 3 }] (12).

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Section: Resultssupporting

confidence: 76%

Metallathiirenes. 3.¹ Thiocarbamoyl and Alkoxythiocarbonyl Complexes of Molybdenum(II) and Tungsten(II)

2001

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“…The CpM‘(CO) 2 Co 2 (CO) 6 (μ 3 -CR) cluster system has been well-studied in both the solid state and in solution, and considerable interest in the past in this cluster concerned the structural isomerism associated with the CpM‘(CO) 2 fragment. − Two distinct rotamers, defined by the orientation of the CpM‘(CO) 2 group relative to the remainder of the cluster, have been observed. Thus, for η 5 -C 5 H 5 and η 5 -C 5 H 4 Me derivatives, the cyclopentadienyl group is distal relative to the carbyne carbon (Chart a) in the solid state.…”

Section: Resultsmentioning

confidence: 99%

Clusters as Ligands. 6. Mixed-Metal Cluster Carboxylates of Titanium and Zirconium Derived from (η⁵-C₅H₅)M‘(CO)₂Co₂(CO)₆(μ₃-CCOOH), M‘ = Mo, W

et al. 1997

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The cluster acid CpM‘(CO)2Co2(CO)6(μ3-CCOOH) (M‘ = Mo, W; Cp = η5-C5H5), 1, has been synthesized in good yield from the protected (CO)9Co3(μ3-CC(O)OR) cluster by metal fragment exchange followed by acid hydrolysis. The protonolysis of group 4 M(IV)(OR)4 (M = Zr, Ti) organic alkoxides with this new cluster acid leads to trimetal cluster M(IV) alkoxycarboxylates. The products, which were isolated in good yield as crystalline substances and characterized spectroscopically as well as crystallographically, are Zr2(μ-OH)2{μ-CpMo(CO)2Co2(CO)6(μ3-CCO2)}2{η2-CpMo(CO)2Co2(CO)6(μ3-CCO2)}4, 2; Ti4(μ3-O)4(OR)2)4{μ-CpM‘(CO)2Co2(CO)6(μ3-CCO2)}4, 3 (M‘ = Mo, R = CH(CH2)3, 3a; M‘ = W, R = CH(CH2)3, 3b; M‘ = Mo, R = C2H5, 3c; M‘ = W, R = C2H5, 3d). Direct comparison of this chemistry with that of [(CO)9Co3(μ3-CCO2)]-, which is of similar size, shows the importance of the electronic properties of the cluster substituent in the metal coordination chemistry of the carboxylate functionality. The exclusive binding of the proximal isomer of the cluster ligand (Cp ring adjacent to the capping carbon) relative to the more stable distal isomer (Cp ring positioned away from the capping carbon) provides definitive evidence for the existence of a cluster electronic effect in the coordination properties of the attached [−CO2]- group. The significantly different chemistry of cluster vs organic ligands arises in part from this electronic effect.

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ChemInform Abstract: CHEMISTRY OF DI‐ AND TRIMETAL COMPLEXES WITH BRIDGING CARBENE OR CARBYNE LIGANDS. PART 10. SYNTHESIS OF DICOBALT‐ AND DIRHODIUM‐TUNGSTEN COMPLEXES WITH μ3‐TOLYLIDYNE GROUPS; CRYSTAL STRUCTURES OF (CO2W(μ3‐CC6H4ME‐4)(CO)8(η‐C5H5)) AND (RH2W(μ3‐CC6H4ME‐4)(ACAC)2(μ‐CO)(CO)2(η‐C5H5)) (ACAC = ACETYLACETONATE)

Chetcuti¹,

Chetcuti²,

Jeffery³

et al. 1982

Chemischer Informationsdienst

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Cited by 29 publications

References 4 publications

Metallathiirenes. 3.¹ Thiocarbamoyl and Alkoxythiocarbonyl Complexes of Molybdenum(II) and Tungsten(II)

Metallathiirenes. 3.¹ Thiocarbamoyl and Alkoxythiocarbonyl Complexes of Molybdenum(II) and Tungsten(II)

Clusters as Ligands. 6. Mixed-Metal Cluster Carboxylates of Titanium and Zirconium Derived from (η⁵-C₅H₅)M‘(CO)₂Co₂(CO)₆(μ₃-CCOOH), M‘ = Mo, W

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Cited by 29 publications

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Metallathiirenes. 3.1 Thiocarbamoyl and Alkoxythiocarbonyl Complexes of Molybdenum(II) and Tungsten(II)

Metallathiirenes. 3.1 Thiocarbamoyl and Alkoxythiocarbonyl Complexes of Molybdenum(II) and Tungsten(II)

Clusters as Ligands. 6. Mixed-Metal Cluster Carboxylates of Titanium and Zirconium Derived from (η5-C5H5)M‘(CO)2Co2(CO)6(μ3-CCOOH), M‘ = Mo, W

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Metallathiirenes. 3.¹ Thiocarbamoyl and Alkoxythiocarbonyl Complexes of Molybdenum(II) and Tungsten(II)

Metallathiirenes. 3.¹ Thiocarbamoyl and Alkoxythiocarbonyl Complexes of Molybdenum(II) and Tungsten(II)

Clusters as Ligands. 6. Mixed-Metal Cluster Carboxylates of Titanium and Zirconium Derived from (η⁵-C₅H₅)M‘(CO)₂Co₂(CO)₆(μ₃-CCOOH), M‘ = Mo, W