Binuclear phosphido-bridged chromium-platinum, molybdenum-platinum, and tungsten-platinum complexes. Synthesis of (CO)4M(.mu.-PPh2)2Pt(PR3) complexes and effect of the M .fwdarw. Pt donor bond on the reactivity of the carbonyl ligands

Powell, John Wesley; Couture, Christian; Gregg, Michael R.; Sawyer, J. F.

doi:10.1021/ic00317a009

Cited by 25 publications

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“…These PdMo distances (2.870(2) and 2.760(1) Å, respectively) are longer than that of 6 . Compared with the reported Mo(0)Pt(II) bond distance of (OC) 4 Mo(μ-PPh 2 ) 2 Pt(PEt 3 ), 2.766(1) Å, the corresponding values of 7 are shorter by 0.1 Å.…”

Section: Discussioncontrasting

confidence: 60%

Reductive Formation of Straight Linear Metal−Metal Bonded Tetranuclear Complexes X−M−Mo−Mo−M−X from X₂M···Mo−Mo···MX₂Supported by Four Tridentate 6-Diphenylphosphino-2-pyridonate Ligands (M = Pd, Pt; X = Cl, Br, I)

1996

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Straight linear tetranuclear complexes have been prepared by using pyphos ligand (pyphos = 6-diphenylphosphino-2-pyridonate), which has unique coordinating sites comprised of three kinds of elements, i.e., phosphine, nitrogen, and oxygen atoms, in almost linear fashion. The starting complex is the quadruply bonded dinuclear molybdenum(II) complex, Mo2(pyphos)4 (1), which was prepared by the reaction of Mo2(OAc)4 with sodium salt of pyphos. Single crystal X-ray analysis revealed that 1 consists of quadruply-bonded Mo2 and trans-arranged diphosphine at both axial position of Mo2 core. Thus, transition metal can be expected to be placed at both axial positions of Mo2 core. Thus, treatment of 1 with Pd(II) and Pt(II) complexes gave rise to tetranuclear complexes of the general formula, Mo2Pd2X4(pyphos)4 (2) and Mo2Pt2X4(pyphos)4 (4) (a: X = Cl; b: X = Br; c: X = I). Single crystal X-ray analysis of 2a, 2b, and 4a revealed the structure of complexes 2 and 4 that consist of M(II)···MoMo···M(II) skeleton supported by four pyphos ligands. They have quadruply-bonded Mo2 core and no bonding between a M(II) atom and a Mo atom. Treatment of 2 and 4 with reducing reagents, photoirradiation, or thermal reduction resulted in the formation of metal−metal bonded tetranuclear complexes Mo2Pd2X2(pyphos)4 (6) and Mo2Pt2X2(pyphos)4 (7) (a: X = Cl; b: X = Br; c: X = I), respectively. All of them were characterized by single crystal X-ray analysis, which revealed that they consist of M(I)-MoMo-M(I) skeleton supported by pyphos ligands. The bond lengths between M(I) and Mo are short enough to be formally regarded as a single M(I)-Mo bond, while the longer Mo−Mo distance compared to that of 1, 2, and 4 indicated that the Mo−Mo bond of 6 and 7 are formally triple (π2δ component). The electrochemical study indicates that all the atoms in the M−Mo−Mo−M system are electronically strongly coupled to allow an effective 2-electron redox process, and thus the chemical reduction of 2 and 4 readily gives 6 and 7, respectively.

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Section: Discussioncontrasting

confidence: 60%

Reductive Formation of Straight Linear Metal−Metal Bonded Tetranuclear Complexes X−M−Mo−Mo−M−X from X₂M···Mo−Mo···MX₂Supported by Four Tridentate 6-Diphenylphosphino-2-pyridonate Ligands (M = Pd, Pt; X = Cl, Br, I)

1996

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“…The Pt-Mo(1) distance of the acetato complex 4b [3.001(1) Å] is 0.02 Å longer than that of the pivalato complex 5b. They are both longer than the Pt-Mo single-bond distance of (CO) 4 Mo(µ-PPh 2 ) 2 Pt(PEt 3 ) [2.766(1) Å] 9 and the Pd-Mo distance of (η-C 5 H 5 )(CO) 2 Mo(µ-PCy 2 )Pd(PCy 2 H) 2 (Cy ) cy-clohexyl) [2.916(2) Å]. 19 No distinct difference is found between these Pt-Mo distances of 5a-c and the Pd-Mo distances reported for 1 [3.025(6) and 2.976(6) Å].…”

Section: Resultsmentioning

confidence: 97%

“…The linear trinuclear Pd···Mo−Mo complex [Mo 2 PdCl 2 (pyphos) 2 (O 2 CCH 3 ) 2 ] 2 ( 1 ) was also synthesized . As an extension of this work, we investigated the interaction of an Mo 2 core with an axial platinum atom, analogous to the bonding interaction between a molybdenum atom and a platinum atom in some cluster complexes. − We describe here the syntheses and structures of linear trinuclear Pt···Mo−Mo complexes of formula [Mo 2 PtX 2 (pyphos) 2 (O 2 CR) 2 ] 2 [R = CH 3 ( 4 ), C(CH 3 ) 3 ( 5 ); X = Cl, Br, I], and the effects on the Mo 2 fragment of this axial interaction.…”

Section: Introductionmentioning

confidence: 99%

Linear Trinuclear Pt···Mo−Mo Complexes [Mo₂PtX₂(pyphos)₂(O₂CR)₂]₂ (X = Cl, Br, I; R = CH₃, C(CH₃)₃; pyphos = 6-(Diphenylphosphino)-2-pyridonate) with an Axial Interaction between the Quadruply Bonded Mo₂ Moiety and the Platinum Atom

1996

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An example of a direct axial interaction of a platinum(II) atom with a Mo(2) core through a uniquely designed tridentate ligand 6-(diphenylphosphino)-2-pyridonate (abbreviated as pyphos) is described. Treatment of PtX(2)(pyphosH)(2) (2a, X = Cl; 2b, X = Br; 2c, X = I) with a 1:1 mixture of Mo(2)(O(2)CCH(3))(4) and [Mo(2)(O(2)CCH(3))(2)(NCCH(3))(6)](2+) (3a) in dichloromethane afforded the linear trinuclear complexes [Mo(2)PtX(2)(pyphos)(2)(O(2)CCH(3))(2)](2) (4a, X = Cl; 4b, X = Br; 4c, X = I). The reaction of [Mo(2)(O(2)CCMe(3))(2)(NCCH(3))(4)](2+) (3b) with 2a-c in dichloromethane afforded the corresponding pivalato complexes [Mo(2)PtX(2)(pyphos)(2)(O(2)CCMe(3))(2)](2) (5a, X = Cl; 5b, X = Br; 5c, X = I), whose bonding nature is discussed on the basis of the data from Raman and electronic spectra as well as cyclic voltammograms. The linear trinuclear structures in 4b and 5a-c were confirmed by NMR studies and X-ray analyses: 4b, monoclinic, space group C2/c, a = 34.733(4) Å, b = 17.81(1) Å, c = 22.530(5) Å, beta = 124.444(8) degrees, V = 11498(5) Å(3), Z = 8, R = 0.060 for 8659 reflections with I > 3sigma(I) and 588 parameters; 5a, triclinic, space group P&onemacr;, a = 13.541(3) Å, b = 17.029(3) Å, c = 12.896(3) Å, alpha = 101.20(2) degrees, beta = 117.00(1) degrees, gamma = 85.47(2) degrees, V = 2599(1) Å(3), Z = 2, R = 0.050 for 8148 reflections with I > 3sigma(I) and 604 parameters; 5b, triclinic, space group P&onemacr;, a = 12.211(2) Å, b = 20.859(3) Å, c = 10.478(2) Å, alpha = 98.88(1) degrees, beta = 112.55(2) degrees, gamma = 84.56(1) degrees, V = 2433.3(8) Å(3), Z = 2, R = 0.042 for 8935 reflections with I > 3sigma(I) and 560 parameters; 5c, monoclinic, space group P2(1)/n, a = 13.359(4) Å, b = 19.686(3) Å, c = 20.392(4) Å, beta = 107.92(2) degrees, V = 5101(2) Å(3), Z = 4, R = 0.039 for 8432 reflections with I > 3sigma(I) and 560 parameters.

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“…1) indicate that the configurations of the two W atoms are opposite and that the molecules differ in the conformations of the phosphine ligands. Notably in molecule 2 the pairs of phenyl rings (1,4) and (33) are closer to being parallel than the corresponding pairs of rings in molecule 1. This arrangement results in a P(l)-Pt-P(2) bond angle of 105.53(9)" which is significantly smaller than the corresponding angle in molecule 1 of 111.74( 9)" (Table 4).…”

Section: ) Has Been Commented On For the System [{W(cp)h(no))-(p-h)]"mentioning

confidence: 91%

Synthesis and site-selective protonation of MoPt and WPt bimetallic complexes

Powell¹,

Sawyer²,

Smith³

1992

J. Chem. Soc., Dalton Trans.

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Binuclear phosphido-bridged chromium-platinum, molybdenum-platinum, and tungsten-platinum complexes. Synthesis of (CO)4M(.mu.-PPh2)2Pt(PR3) complexes and effect of the M .fwdarw. Pt donor bond on the reactivity of the carbonyl ligands

Cited by 25 publications

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Reductive Formation of Straight Linear Metal−Metal Bonded Tetranuclear Complexes X−M−Mo−Mo−M−X from X₂M···Mo−Mo···MX₂Supported by Four Tridentate 6-Diphenylphosphino-2-pyridonate Ligands (M = Pd, Pt; X = Cl, Br, I)

Reductive Formation of Straight Linear Metal−Metal Bonded Tetranuclear Complexes X−M−Mo−Mo−M−X from X₂M···Mo−Mo···MX₂Supported by Four Tridentate 6-Diphenylphosphino-2-pyridonate Ligands (M = Pd, Pt; X = Cl, Br, I)

Linear Trinuclear Pt···Mo−Mo Complexes [Mo₂PtX₂(pyphos)₂(O₂CR)₂]₂ (X = Cl, Br, I; R = CH₃, C(CH₃)₃; pyphos = 6-(Diphenylphosphino)-2-pyridonate) with an Axial Interaction between the Quadruply Bonded Mo₂ Moiety and the Platinum Atom

Synthesis and site-selective protonation of MoPt and WPt bimetallic complexes

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Binuclear phosphido-bridged chromium-platinum, molybdenum-platinum, and tungsten-platinum complexes. Synthesis of (CO)4M(.mu.-PPh2)2Pt(PR3) complexes and effect of the M .fwdarw. Pt donor bond on the reactivity of the carbonyl ligands

Cited by 25 publications

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Reductive Formation of Straight Linear Metal−Metal Bonded Tetranuclear Complexes X−M−Mo−Mo−M−X from X2M···Mo−Mo···MX2Supported by Four Tridentate 6-Diphenylphosphino-2-pyridonate Ligands (M = Pd, Pt; X = Cl, Br, I)

Reductive Formation of Straight Linear Metal−Metal Bonded Tetranuclear Complexes X−M−Mo−Mo−M−X from X2M···Mo−Mo···MX2Supported by Four Tridentate 6-Diphenylphosphino-2-pyridonate Ligands (M = Pd, Pt; X = Cl, Br, I)

Linear Trinuclear Pt···Mo−Mo Complexes [Mo2PtX2(pyphos)2(O2CR)2]2 (X = Cl, Br, I; R = CH3, C(CH3)3; pyphos = 6-(Diphenylphosphino)-2-pyridonate) with an Axial Interaction between the Quadruply Bonded Mo2 Moiety and the Platinum Atom

Synthesis and site-selective protonation of MoPt and WPt bimetallic complexes

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Reductive Formation of Straight Linear Metal−Metal Bonded Tetranuclear Complexes X−M−Mo−Mo−M−X from X₂M···Mo−Mo···MX₂Supported by Four Tridentate 6-Diphenylphosphino-2-pyridonate Ligands (M = Pd, Pt; X = Cl, Br, I)

Reductive Formation of Straight Linear Metal−Metal Bonded Tetranuclear Complexes X−M−Mo−Mo−M−X from X₂M···Mo−Mo···MX₂Supported by Four Tridentate 6-Diphenylphosphino-2-pyridonate Ligands (M = Pd, Pt; X = Cl, Br, I)

Linear Trinuclear Pt···Mo−Mo Complexes [Mo₂PtX₂(pyphos)₂(O₂CR)₂]₂ (X = Cl, Br, I; R = CH₃, C(CH₃)₃; pyphos = 6-(Diphenylphosphino)-2-pyridonate) with an Axial Interaction between the Quadruply Bonded Mo₂ Moiety and the Platinum Atom