Organotransition-metal complexes of multidentate ligands. 10. Steric vs. electronic control on formation of six- and seven-coordinate carbonyl halides of molybdenum(II) and tungsten(II)

Shiu, Kom-Bei; Liou, Kuen Song.; Wang, Sue Lein; Wei, Shi Chen

doi:10.1021/om00117a022

Cited by 41 publications

(10 citation statements)

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“…It is therefore surprising that for the present compound no decomposition, e.g. decarbonylation (Shiu et al, 1990) was encountered when crystals were briefly exposed to oxygen, room temperature and light during set-up of the X-ray diffraction experiment. The chelating bis(4-methylthiazol-2-yl)methane ligand may exert additional stabilizing properties when compared to the ligands used in the literature.…”

Section: Data Collectionmentioning

confidence: 80%

“…For related compounds, see: Baker et al (1986); Moss & Smith (1983); Stiddard (1962); Szymanska-Buzar (1989); Tripathi et al (1976). For related structures, see: Baker et al (1996Baker et al ( , 2000; Drew et al (1988Drew et al ( , 1995; Hillhouse et al (1982); Shiu et al (1990). For the isolation of the title compound, see: Strasser et al (2009).…”

Section: Related Literaturementioning

confidence: 99%

“…Hillhouse et al (1982) report coordination of a tetraarylphosphazide (PhNNNPPh 3 ) to a dibromotricarbonyltungsten fragment which is different from the title compound and the structures mentioned here in that it contains a set of cis-bromo ligands, possibly caused by the smaller bite angle of the tetraarylphosphazide (N-W-N angle of 56.7 (2)° as opposed to the N1 -W1-N2 angle measuring 83.3 (2)° in the title compound). Finally, a geometrically very similar complex to the one reported here but utilizing a bis(azolyl)methane ligand was prepared by Shiu et al, (1990)…”

Section: Complexes Of the Type [Wxmentioning

confidence: 99%

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[Bis(4-methyl-1,3-thiazol-2-yl-κN)methane]tricarbonyldichloridotungsten(II)

2011

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The title compound, [WCl2(C9H10N2S2)(CO)3], is a heptacoordinate tungsten(II) complex with a capped–octahedral coordination sphere in which one CO ligand caps a face formed by a chloro ligand and the two other carbonyls. The chloro ligands are mutually trans positioned at an angle of 156.98 (7)°. The chelating bis(4-methyl-1,3-thiazol-2-yl)methane ligand coordinates with the imine N atoms. In the crystal, molecules are linked into chains parallel to [201] by weak C—H⋯O contacts between the CH2 group of the bis(4-methylthiazol-2-yl)methane ligand and the O atom of the capping CO group.

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Section: Data Collectionmentioning

confidence: 80%

Section: Related Literaturementioning

confidence: 99%

Section: Complexes Of the Type [Wxmentioning

confidence: 99%

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[Bis(4-methyl-1,3-thiazol-2-yl-κN)methane]tricarbonyldichloridotungsten(II)

2011

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“…[1][2][3][4][5] Oxidation to tungsten(II) is most commonly achieved by addition of elemental halogens to zero-valent carbonyl complexes containing at least one non-carbonyl donor ligand. 6,7 Halogenation by iodine, 8 bromine, 9 and chlorine 10 is common in the literature. Oxidative decarboxylation with hydrofluoric acid 11 or addition of fluoride to a neutral tungsten(II) dicarbonyl complex 12 can provide access to the less common tungsten fluoride complexes.…”

Section: Introductionmentioning

confidence: 99%

“…[31][32][33][34] The amine can be deprotonated to give an anionic tridentate amido ligand (PNP − ). We report here coordination of P H NP to a d 6 tungsten center and subsequent oxidation to form cationic and neutral d 4 tungsten(II) hydride and halide complexes.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and oxidation of d6 tungsten pincer complexes: a complete series of tungsten(ii) hydridocarbonyl and halocarbonyl pincer complexes

2012

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Reaction of the neutral P(H)NP ligand [HN(SiMe(2)CH(2)PPh(2))(2)] with tungsten hexacarbonyl resulted in coordination of P(H)NP through both phosphorus donor atoms to form the tungsten complex [W(P(HN)P)(CO)(4)] (1). Reaction of P(H)NP with tris(acetonitrile)tricarbonyl tungsten gave both facial and meridional tridentate isomers [W(P(H)NP)(CO)(3)] (2-fac and 3-mer). These three d(6) tungsten complexes could be interconverted under appropriate conditions. The thermodynamically favored isomer 3 was protonated to form seven-coordinate [W(P(H)NP)(CO)(3)H][BF(4)] (4). A related series of cationic tungsten(II) halide complexes was synthesized, [W(P(H)NP)(CO)(3)X](+) (6, X = I; 7, X = Br; 8, X = Cl; 9, X = F), by various routes. All of the tungsten(II) complexes underwent deprotonation at the amine site of the P(H)NP ligand when triethylamine was added, resulting in neutral seven-coordinate complexes. Variable temperature (1)H, (31)P{(1)H}, and (13)C{(1)H} NMR spectroscopy showed fluxional behavior for all the seven-coordinate complexes reported here. Analysis of IR and NMR spectroscopic data showed trends through the series of coordinated halides. Crystal structures of tetracarbonyl 1, meridional tricarbonyl 3, and cationic hydride 4 were determined to confirm the coordination mode of the P(H)NP ligand.

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Synthesis and Reactivity of Group 6 Metal Carbonyl Complexes with Bis(pyrazol‐1‐yl)methanes Modified by the Vinyltin Groups

et al. 2009

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Diphenyl(vinyl)stannylbis(3,5-dimethylpyrazol-1-yl)methane and diphenyl(vinyl)stannylbis(3,4,5-trimethylpyrazol-1-yl)methane have been synthesized by the reaction of bis(3,5-dimethylpyrazol-1-yl)methyl or bis(3,4,5trimethylpyrazol-1-yl)methyllithium with diphenyl(vinyl)tin iodide. Treatment of these bis(pyrazol-1-yl)methanes modified by the vinyltin groups with M(CO) 5 THF (M＝Mo and W) in refluxing THF resulted in new heterobimetallic complexes R 3 SnCHPz 2 M(CO) 3 (R 3 Sn represents trivinyltin or diphenyl(vinyl)tin, and Pz represents substituted pyrazol-1-yl), in which a vinyl group bonds to the molybdenum or tungsten atom in η 2 -fashion to lead to bis(pyrazol-1-yl)methanes acting as a tridentate κ 3 -(π,N,N) ligand. Reaction of (CH 2 ＝ CH) 3 SnCH(3,5-Me 2 Pz) 2 W(CO) 3 and Ph 2 (CH 2 ＝CH)SnCH(3,5-Me 2 Pz) 2 W(CO) 3 with I 2 has been investigated. The former gave a complex CH 2 (3,5-Me 2 Pz) 2 W(CO) 4 , while the latter yielded a four-membered heterometallocyclic complex CH(3,5-Me 2 Pz) 2 W(CO) 3 I with the loss of the organotin group. Treatment of this four-membered heterometallocyclic complex with PhSNa led to the iodide anion replaced by the thiophenolate anion to give a complex CH(3,5-Me 2 Pz) 2 W(CO) 3 SPh.

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Organotransition-metal complexes of multidentate ligands. 10. Steric vs. electronic control on formation of six- and seven-coordinate carbonyl halides of molybdenum(II) and tungsten(II)

Cited by 41 publications

References 2 publications

[Bis(4-methyl-1,3-thiazol-2-yl-κN)methane]tricarbonyldichloridotungsten(II)

[Bis(4-methyl-1,3-thiazol-2-yl-κN)methane]tricarbonyldichloridotungsten(II)

Synthesis and oxidation of d6 tungsten pincer complexes: a complete series of tungsten(ii) hydridocarbonyl and halocarbonyl pincer complexes

Synthesis and Reactivity of Group 6 Metal Carbonyl Complexes with Bis(pyrazol‐1‐yl)methanes Modified by the Vinyltin Groups

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