Bis(triphenylphosphine)palladium Cycloheptadienynylium Tetrafluoroborate:  A Palladium Complex of Tropyne

Klosin, Jerzy; Abboud, Khalil A.; Jones, W. M.

doi:10.1021/om9600396

Cited by 12 publications

(3 citation statements)

References 22 publications

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“…As expected on the basis of atomic radii, the M−C and M−P bonds in 5b are ca. 0.15 Å longer than those in 4b ; the Pd−C distances compare with those reported for the 3,5-cycloheptadien-1-yne complex [Pd(η 2 -C 7 H 6 )(PPh 3 ) 2 ] (2.031(4) and 2.039(4) Å) . The P−M−P angles are similar, 122.19(5)° for 4b and 119.…”

Section: Resultssupporting

confidence: 67%

Preparation of Benzyne Complexes of Group 10 Metals by Intramolecular Suzuki Coupling ofortho-Metalated Phenylboronic Esters: Molecular Structure of the First Benzyne-Palladium(0) Complex

et al. 2002

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A series of nickel(II) and palladium(II) aryl complexes substituted in the ortho position of the aromatic ring by a (pinacolato)boronic ester group, [MBr[o-C(6)H(4)B(pin)]L(2)] (M = Ni, L(2) = 2PPh(3) (2a), 2PCy(3) (2b), 2PEt(3) (2c), dcpe (2d), dppe (2e), and dppb (2f); M = Pd, L(2) = 2PPh(3) (3a), 2PCy(3) (3b), and dcpe (3d)), has been prepared. Many of these complexes react readily with KO(t)Bu to form the corresponding benzyne complexes [M(eta(2)-C(6)H(4))L(2)] (M = Ni, L(2) = 2PPh(3) (4a), 2PCy(3) (4b), 2PEt(3) (4c), dcpe (4d); M = Pd, L(2) = 2PCy(3) (5b)). This reaction can be regarded as an intramolecular version of a Suzuki cross-coupling reaction, the driving force for which may be the steric interaction between the boronic ester group and the phosphine ligands present in the precursors 2 and 3. Complex 3d also reacts with KO(t)Bu, but in this case disproportionation of the initially formed eta(2)-C(6)H(4) complex (5d) leads to a 1:1 mixture of a novel dinuclear palladium(I) complex, [(dcpe)Pd(mu(2)-C(6)H(4))Pd(dcpe)] (6), and a 2,2'-biphenyldiyl complex, [Pd(2,2'-C(6)H(4)C(6)H(4))(dcpe)] (7d). Complexes 2a, 3b, 3d, 4b, 5b, 6, and 7d have been structurally characterized by X-ray diffraction; complex 5b is the first example of an isolated benzyne-palladium(0) species.

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Section: Resultssupporting

confidence: 67%

Preparation of Benzyne Complexes of Group 10 Metals by Intramolecular Suzuki Coupling ofortho-Metalated Phenylboronic Esters: Molecular Structure of the First Benzyne-Palladium(0) Complex

et al. 2002

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“…1 H NMR (400 MHz, CDCl 3 , 25 °C): δ 7.45–7.38 (m, 6H, H Ph ), 7.38–7.28 (m, 24H, H Ph ), 5.51 (t, J = 2.1 Hz, 5H, H Cp ). 13 C{ 1 H} NMR (101 MHz, CDCl 3 , 25 °C): δ 133.73 (observed as virtual triplets (vt) due to virtual coupling [ 56 , 110 ], J = 6.1 Hz, C Ph,ortho ), 131.57 (s, C Ph,para ), 130.65 (vt, 1 J (P,C ipso ) = 24.5 Hz), 128.97 (vt, J = 5.6 Hz, C Ph,meta ), 104.27 (t, J = 2.3 Hz, C Cp ). 13 C{ 1 H, gated decoupling mode} NMR (101 MHz, CDCl 3 , 25 °C): δ 133.73 (d, J CH = 163 Hz, C Ph,ortho ), 131.57 (d, J CH = 163 Hz, C Ph,para ), the signals for ipso -C of PPh 3 were not clearly observed, 128.97 (d, J CH = 165 Hz, C Ph,meta ), 104.27 (d, J CH = 178 Hz, C Cp ).…”

Section: Methodsmentioning

confidence: 99%

“…The resulting reaction mixture was concentrated to 5 mL under vacuum. Addition of diethyl ether (20 mL) formed a purple precipitate, which was collected, washed with diethyl ether (2 × 10 mL), and dried (8 h) under vacuum to afford complex 1 as a purple powder (327 mg, 85.3% [56,110], J = 6.1 Hz, C Ph,ortho ), 131.57 (s, C Ph,para ), 130.65 (vt, 1 J(P,C ipso ) = 24.5 Hz), 128.97 (vt, J = 5.6 Hz, C Ph,meta ), 104.27 (t, J = 2.3 Hz, C Cp ). 13…”

Section: Synthesis Of Palladium Complexesmentioning

confidence: 99%

Novel Route to Cationic Palladium(II)–Cyclopentadienyl Complexes Containing Phosphine Ligands and Their Catalytic Activities

et al. 2023

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The Pd(II) complexes [Pd(Cp)(L)n]m[BF4]m were synthesized via the reaction of cationic acetylacetonate complexes with cyclopentadiene in the presence of BF3∙OEt2 (n = 2, m = 1: L = PPh3 (1), P(p-Tol)3, tris(ortho-methoxyphenyl)phosphine (TOMPP), tri-2-furylphosphine, tri-2-thienylphosphine; n = 1, m = 1: L = dppf, dppp (2), dppb (3), 1,5-bis(diphenylphosphino)pentane; n = 1, m = 2 or 3: 1,6-bis(diphenylphosphino)hexane). Complexes 1–3 were characterized using X-ray diffractometry. The inspection of the crystal structures of the complexes enabled the recognition of (Cp–)⋯(Ph-group) and (Cp–)⋯(CH2-group) interactions, which are of C–H…π nature. The presence of these interactions was confirmed theoretically via DFT calculations using QTAIM analysis. The intermolecular interactions in the X-ray structures are non-covalent in origin with an estimated energy of 0.3–1.6 kcal/mol. The cationic palladium catalyst precursors with monophosphines were found to be active catalysts for the telomerization of 1,3-butadiene with methanol (TON up to 2.4∙104 mol 1,3-butadiene per mol Pd with chemoselectivity of 82%). Complex [Pd(Cp)(TOMPP)2]BF4 was found to be an efficient catalyst for the polymerization of phenylacetylene (PA) (catalyst activities up to 8.9 × 103 gPA·(molPd·h)−1 were observed)

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The Reactivity of Complexes of Nickel(0) and Platinum(0) Containing Benzyne and Related Small‐Ring Alkynes

Bennett

Wenger

1997

Chem. Ber.

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The preparation and reactivities of cyclohexyne and aryne complexes of platinum@) and nickel(0) are reviewed. These complexes undergo insertions with unsaturated molecules such as alkenes, alkynes, isocyanides, CO and C 0 2 . I n the case of the nickel-benzyne complexes, consecutive insertions are observed with alkynes, leading to substituted naphthalenes with good regioselectivities. A possible mechanism for these double insertions, based on a combination of steric and electronic factors, is discussed in detail.

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Bis(triphenylphosphine)palladium Cycloheptadienynylium Tetrafluoroborate: A Palladium Complex of Tropyne

Abstract: Palladium complexes of cyclohepta-3,5-dien-1-yne (4) and cyclohepta-1,5-dien-3-yne (5) have been prepared and converted to a palladium complex of tropyne (6) by treatment with triphenylcarbenium tetrafluoroborate.

Cited by 12 publications

References 22 publications

Preparation of Benzyne Complexes of Group 10 Metals by Intramolecular Suzuki Coupling ofortho-Metalated Phenylboronic Esters: Molecular Structure of the First Benzyne-Palladium(0) Complex

Preparation of Benzyne Complexes of Group 10 Metals by Intramolecular Suzuki Coupling ofortho-Metalated Phenylboronic Esters: Molecular Structure of the First Benzyne-Palladium(0) Complex

Novel Route to Cationic Palladium(II)–Cyclopentadienyl Complexes Containing Phosphine Ligands and Their Catalytic Activities

The Reactivity of Complexes of Nickel(0) and Platinum(0) Containing Benzyne and Related Small‐Ring Alkynes

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