Octahedral metal carbonyls 75. ‘Directed’ synthesis of tungsten carbonyl complexes of alkenyldiphenylphosphines

Wang, I-Hsiung; Wermer, Paul H.; Dobson, Charles B.; Dobson, Gerard R.

doi:10.1016/s0020-1693(00)82991-6

Cited by 5 publications

(2 citation statements)

References 22 publications

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“…Air-sensitive substances were sealed in capillaries at 1 bar of argon. CoCH 3 (PMe 3 ) 4 , trimethylphosphine, allyldiphenylphosphine (Ph 2 PCH 2 -CHCH 2 ), 3-butenyldiphenylphosphine (Ph 2 P(CH 2 ) 2 -CHCH 2 ), and 4-pentenyldiphenylphosphine (Ph 2 P(CH 2 ) 3 -CHCH 2 ) were synthesized according to literature methods. The compounds benzene- d 6 and THF- d 8 were purchased from Sigma-Aldrich.…”

Section: Methodsmentioning

confidence: 99%

“…The addition of terminal alkenyl-diphenylphosphines to electron-rich transition metals establishes various coordination modes (Chart ), such as M = Ru(II), Zr(II), and W(0), and frequently results in κ 3 ,η 2 - P,C,C coordination. Fewer examples have been described with M = Ru(II), Rh(I), Ir(I), and Pd(II), for simple κ 1 - P coordination or a π-allylic motif (κ 4 , η 3 - P,C,C,C ) with M = Ru(II), , Mn(0), and Os(IV) .…”

Section: Introductionmentioning

confidence: 99%

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Cobalt-Promoted Tandem C(sp²)–H Activation and C–C Coupling of Vinyldiphenylphosphine: σ- vs π-Coordination Modes within Cyclometalation

2015

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We have studied the reactivity of a series of terminal alkenyldiphenylphosphines {Ph2P(CH2) n -CHCH2), n = 0, 1, 2, 3} under mild conditions (−70 °C) in reaction with univalent Co(I). Methane and ethane elimination occurs when different olefinic P,C-coordination modes are established. Subsequent C–H activation and C–C coupling take place in the reaction of Co(CH3)(PMe3)4 with vinyldiphenylphosphine (1:2 molar ratio) to form a novel anionic P,C,P-type ligand with asymmetric ring sizes attached to the cobalt center of (PMe3)2Co{κ3-(P,C,P)-(Ph2)CH2CHCH-CH(PPh2)} (1). X-ray study of 1 revealed that the complex has a unique cyclometalated structure of a three-membered ring within the newly assembled bis-phosphine ligand. Cyclometalation via selective vinyl-group C(sp2)–H activation of stoichiometric amounts allyl-diphenylphosphine with Co(CH3)(PMe3)4 afforded for the first time σ-allyl coordination incorporated in a five-membered cobaltacycle of (PMe3)2Co{κ2(P,C)-HCCHCH2PPh2} (2); subsequent C–C coupling is not observed. By contrast, equimolar mixtures of pentenyl-diphenylphosphine and Co(CH3)(PMe3)4 afforded a η3-coordinated π-allyl complex of composition (PMe3)2Co{η3-κ4-(P,C,C,C)-H2CCH-CH(CH2)2PPh2} (3). All unprecedented complexes were characterized by multinuclear NMR spectroscopy and X-ray diffraction, and their mechanisms of formation are discussed.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Cobalt-Promoted Tandem C(sp²)–H Activation and C–C Coupling of Vinyldiphenylphosphine: σ- vs π-Coordination Modes within Cyclometalation

2015

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Tris(dibenzo[a,d]cycloheptenyl)phosphane: A Bulky Monodentate or Tetrapodal Ligand

Fischbach

Rüegger

2007

Eur J Inorg Chem

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The tetradendate phosphane tris(5H‐dibenzo[a,d]cyclohepten‐5‐yl)phosphane (trop3P, 1) was synthesized from tris(trimethylsilyl)phosphane and 5‐chloro‐5H‐dibenzo[a,d]cycloheptene. Sulfurization of 1 with elemental sulfur led to trop3P=S. Complexes of 1 with AgI, AuI, RhI, IrI, and PdII were prepared. The structures of trop3P (1), trop3P=S (2), [AgCl(trop3P)] (3), [Au(trop3P)(MeCN)]PF6 (5), [RhCl(trop3P)] (6) and [Pd(trop3P)(H2O)](OTf)2 (9) were determined by X‐ray diffraction studies. In the coinage metal complexes, 1 serves as monodentate extremely bulky κ1‐phosphane ligand (cone angle ca. 250°). In the RhI, IrI, and PdII complexes, 1 acts as tetradendate ligand. CP MAS NMR spectroscopy shows that the span of the chemical shift tensor increases in 7, 6, and 9 in this order (Ω = 310 ppm, 410 ppm, 465 ppm) and contains two strongly deshielded components, which are responsible for the unusual high frequency isotropic shift of the 31P resonances. This property correlates inversely with the metal to olefin backbonding (M→C=Ctrop) and δ(31P) decreases with increasing M→C=Ctrop in the order 9 (δ = 260 ppm) > 7 (δ = 196 ppm) > 6 (δ = 135 ppm) > 3 (δ = –30.9 ppm). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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π-Complexes of Chromium, Molybdenum and Tungsten, Excluding those of Cyclopentadienyls and Arenes

Whiteley

1995

Comprehensive Organometallic Chemistry II

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Octahedral metal carbonyls 75. ‘Directed’ synthesis of tungsten carbonyl complexes of alkenyldiphenylphosphines

Cited by 5 publications

References 22 publications

Cobalt-Promoted Tandem C(sp²)–H Activation and C–C Coupling of Vinyldiphenylphosphine: σ- vs π-Coordination Modes within Cyclometalation

Cobalt-Promoted Tandem C(sp²)–H Activation and C–C Coupling of Vinyldiphenylphosphine: σ- vs π-Coordination Modes within Cyclometalation

Tris(dibenzo[a,d]cycloheptenyl)phosphane: A Bulky Monodentate or Tetrapodal Ligand

π-Complexes of Chromium, Molybdenum and Tungsten, Excluding those of Cyclopentadienyls and Arenes

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Octahedral metal carbonyls 75. ‘Directed’ synthesis of tungsten carbonyl complexes of alkenyldiphenylphosphines

Cited by 5 publications

References 22 publications

Cobalt-Promoted Tandem C(sp2)–H Activation and C–C Coupling of Vinyldiphenylphosphine: σ- vs π-Coordination Modes within Cyclometalation

Cobalt-Promoted Tandem C(sp2)–H Activation and C–C Coupling of Vinyldiphenylphosphine: σ- vs π-Coordination Modes within Cyclometalation

Tris(dibenzo[a,d]cycloheptenyl)phosphane: A Bulky Monodentate or Tetrapodal Ligand

π-Complexes of Chromium, Molybdenum and Tungsten, Excluding those of Cyclopentadienyls and Arenes

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Product

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Cobalt-Promoted Tandem C(sp²)–H Activation and C–C Coupling of Vinyldiphenylphosphine: σ- vs π-Coordination Modes within Cyclometalation

Cobalt-Promoted Tandem C(sp²)–H Activation and C–C Coupling of Vinyldiphenylphosphine: σ- vs π-Coordination Modes within Cyclometalation