A series of edge-sharing bioctahedral, M-M bonded molecules:  nonmonotonic bond length variation and its interpretation

Chakravarty, Akhil R.; Cotton, F. Albert; Diebold, Michael P.; Lewis, Diane B.; Roth, Wiesław J.

doi:10.1021/ja00265a022

Cited by 46 publications

(24 citation statements)

References 3 publications

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“…While the M-P bond lengths of niobium and tantalum phosphine complexes are in the range of 2.59 to 2.67 Å [14, 15,30,32,33,34,35,36], 1؊5 exhibit rather long M-P bonds [Ta(1)-P(1) bonds of 2.651(3)Ϫ2.704(1) Å ; Nb(1)-P(1) bonds of 2.642(2)Ϫ2.691(1) Å ] which is possibly due to the steric influence of the chlorine ligands or the trans effect of the Cp* ligand. These distances are longer than the sum of the covalent radii of Ta or Nb and P [37].…”

Section: Molecular Structures Of [Cp*tacl 4 ] and 1؊5mentioning

confidence: 99%

Organometallic Niobium and Tantalum Complexes with Primary Phosphine Ligands: Syntheses and Molecular Structures of [CpMCl4(PH2R)] (M = Nb, Ta; Cp = C5Me5;R = But, Ad, Cy, Ph, 2, 4, 6-Me3C6H2 (Mes))

Blaurock

Hey‐Hawkins

2002

Z. anorg. allg. Chem.

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The reaction of [Cp*MCl 4 ] (M ϭ Nb, Ta; Cp* ϭ C 5 Me 5 ) with PH 2 R in toluene at room temperature gives the primary phosphine complexes [Cp*MCl 4 (PH 2 R)] [Cp* ϭ C 5 Me 5 ; M ϭ Nb: R ϭ Bu t (1a), Ad (2a), Cy (3a), Ph (4a), 2,4,6-Me 3 C 6 H 2 (Mes) (5a); M ϭ Ta: R ϭ Bu t (1b), Ad (2b), Cy (3b), Ph (4b), Mes (5b)] in high yield. 1؊5 were characterized spectroscopically (NMR, IR, MS) and by Metallorganische Niob-und Tantal-Komplexe mit primären Phosphanliganden: Synthese und Molekülstrukturen von [Cp*MCl 4 (PH 2 R)] (M ‫؍‬ Nb, Ta; Cp* ‫؍‬ C 5 Me 5 ; R ‫؍‬ Bu t , Ad, Cy, Ph, 2,4,6-Me 3 C 6 H 2 (Mes)) Inhaltsübersicht. Die Komplexe [Cp*MCl 4 ] (M ϭ Nb, Ta; Cp* ϭ C 5 Me 5 ) reagieren bei Raumtemperatur in Toluol mit den primären Phosphanen PH 2 R unter glatter Bildung der Verbindungen [Cp* MCl 4 (PH 2 R)] [Cp* ϭ C 5 Me 5 ; M ϭ Nb: R ϭ Bu t (1a), Ad (2a), Cy

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Section: Molecular Structures Of [Cp*tacl 4 ] and 1؊5mentioning

confidence: 99%

Organometallic Niobium and Tantalum Complexes with Primary Phosphine Ligands: Syntheses and Molecular Structures of [CpMCl4(PH2R)] (M = Nb, Ta; Cp = C5Me5;R = But, Ad, Cy, Ph, 2, 4, 6-Me3C6H2 (Mes))

Blaurock

Hey‐Hawkins

2002

Z. anorg. allg. Chem.

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“…[16][17][18][19][20][21][22][23] Single-bonded Ru(III)-Ru(III) dimers containing other bridging ligands (RCO 2 -, OH -, and dppm/Cl -) have been reported. [24][25][26] Experimental Details General Information. All reagents were purchased from Aldrich and used without further purification.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Bis-Thiolato-Bridged Ru(III) Dimers. The Crystal Structure of [Ru(H₂edta)(μ-SC₆H₅)]₂

et al. 2000

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“…The complex has a dinuclear structure with two chloride bridges and two other head-to-tail axial PN bridges. The two metal centres are in a slightly distorted octahedral geometry as a consequence of the bridge strain, which is exemplified by the N(1)ϪRu(1)ϪCl (1) (2) 2.3987(8) P(1)ϪRu(1)ϪCl(1) 89.47(3) Ru(1)ϪCl(1A) 2.4387(8) P(2)ϪRu(1)ϪCl (1) 93.40(3) P(1)ϪC (25) 1.832(3) N(1)ϪRu(1)ϪCl (2) 87.43(7) P(1)ϪC (19) 1.840(3) P(1)ϪRu(1)ϪCl (2) 95.57(3) P(1)ϪC (33) 1.861(3) P(2)ϪRu(1)ϪCl (2) 92.04(3) P(2)ϪC (13) 1.827(3) Cl(1)ϪRu(1)ϪCl (2) 171.77(3) P(2)ϪC (1) 1.848(3) N(1)ϪRu(1)ϪCl(1A) 82.80(7) P(2)ϪC (7) 1.852(3) P(1)ϪRu (1) (2) N (2)ϪRu (1)ϪP (1) 68.74(6) Ru(1)ϪN (4) 2.160(2) N(4)ϪRu(1)ϪP (2) 68.59(6) Ru(1)ϪN (2) 2.173(2) N(6)ϪRu(1)ϪP(3) 69.04(7) Ru(1)ϪP (1) 2.2954 (8) N (2)ϪC (13)ϪP (1) 105.50(18) Ru(1)ϪP (3) 2.2990(9) N(6)ϪC (45)ϪP (3) 104.58(18) Ru(1)ϪP (2) 2.2995 (8) N (4)ϪC (29)ϪP (2) 105.28 (18) The Ru(1)ϪRu(1A) distance is only 3.398 Å and is intermediate between those typically observed in complexes with [17] The presence of the two additional PCN bridges can lead to shortening of this distance, a situation that has been observed in other dinuclear Ru derivatives with additional short bridges. [18] In addition, the distances between each of the chloride bridging ligands and each of the ruthenium atoms are asymmetric, with d[Ru(1)ϪCl(1)] ϭ 2.3878 Å and d [Ru(1A)ϪCl (1)] ϭ 2.4387...…”

Section: Reaction Of Pphmentioning

confidence: 93%

Synthesis and Structure of New (Polyphosphane)ruthenium Complexes with the Hemilabile Ligand 2‐(Diphenylphosphanyl)‐1‐methyl‐1H‐imidazole − An Unexpected Rearrangement of [RuCl₂(PN)(PPh₃)₂]

et al. 2004

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Several RuII complexes containing the potentially bidentate ligand 2‐(diphenylphosphanyl)‐1‐methyl‐1H‐imidazole [PPh2MeIm (PN)] have been synthesised and characterised. Reaction of the ligand with [RuCl2(PPh3)3] in different molar ratios led to the formation of the complexes trans,mer‐[RuCl2(PPh3)2(κ2‐P,N−PPh2MeIm)] (1), fac‐[RuCl(PPh3)(κ2‐P,N‐PPh2MeIm)2]Cl (2a), mer‐[RuCl(PPh3)(κ2‐P,N‐PPh2MeIm)2]Cl (2b), fac‐[RuCl(κ1‐P‐PPh2MeIm)(κ2‐P,N‐PPh2MeIm)2]Cl (3a), and mer‐[RuCl(κ1‐P‐PPh2MeIm)(κ2‐PN‐PPh2MeIm)2]Cl (3b). Complex 1 evolves in solution to 2a, 2b and the dinuclear species [(PPh3)(κ1‐P‐PPh2MeIm)ClRu(μ‐Cl)2Ru(PPh3)(κ1‐P‐PPh2MeIm)Cl] (4a), [(PPh3)ClRu(μ‐Cl)2(μ2‐P,N‐PPh2MeIm)2Ru(PPh3)Cl] (4b), and [(PPh3)(κ2‐P,N‐PPh2MeIm)ClRu(μ‐Cl)2Ru(PPh3)(κ2‐P,N‐PPh2MeIm)Cl] (4c). It is proposed that the formation of the dinuclear derivatives involves an Ru−N bond‐breaking step that demonstrates the hemilabile behaviour of the ligand. When 2 equiv. of the PN ligand were added to [RuCl2(cod)(bpzm)] [cod = 1,5‐cyclooctadiene, bpzm = bis(pyrazol‐1‐yl)methane], the complex cis‐P‐[RuCl2(κ1‐PPh2MeIm)(κ2‐PPh2MeIm)] (5) was formed as the only product. The derivatives [Ru(κ2‐PPh2MeIm)3]X2 [(X = PF6 (6), BF4 (7)] were obtained upon treatment of [RuCl2(arene)]2 (arene = p‐cymene, benzene) with 2 equiv. of the corresponding silver salts and the PN ligand. Both the fac (6a, 7a) and mer (6b, 7b) forms were obtained. Two new hydride complexes were also synthesised: mer‐[RuHClL2(κ2‐PPh2MeIm)] [L = PPh3 (8) or κ1‐PN (9)] by reaction of the PN ligand with [RuHCl(PPh3)3] or [RuHCl(cod)(bpzm)], respectively. The molecular structure of 4b and fac‐7a was solved by an X‐ray diffraction study. Complex 4b has a dinuclear structure with two chloride bridges and two head‐to‐tail PN bridges. The derivative fac‐7a is mononuclear. Both enantiomers — Δ and Λ — were observed in the same unit cell. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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A series of edge-sharing bioctahedral, M-M bonded molecules: nonmonotonic bond length variation and its interpretation

Cited by 46 publications

References 3 publications

Organometallic Niobium and Tantalum Complexes with Primary Phosphine Ligands: Syntheses and Molecular Structures of [CpMCl4(PH2R)] (M = Nb, Ta; Cp = C5Me5;R = But, Ad, Cy, Ph, 2, 4, 6-Me3C6H2 (Mes))

Organometallic Niobium and Tantalum Complexes with Primary Phosphine Ligands: Syntheses and Molecular Structures of [CpMCl4(PH2R)] (M = Nb, Ta; Cp = C5Me5;R = But, Ad, Cy, Ph, 2, 4, 6-Me3C6H2 (Mes))

Synthesis of Bis-Thiolato-Bridged Ru(III) Dimers. The Crystal Structure of [Ru(H₂edta)(μ-SC₆H₅)]₂

Synthesis and Structure of New (Polyphosphane)ruthenium Complexes with the Hemilabile Ligand 2‐(Diphenylphosphanyl)‐1‐methyl‐1H‐imidazole − An Unexpected Rearrangement of [RuCl₂(PN)(PPh₃)₂]

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A series of edge-sharing bioctahedral, M-M bonded molecules: nonmonotonic bond length variation and its interpretation

Cited by 46 publications

References 3 publications

Organometallic Niobium and Tantalum Complexes with Primary Phosphine Ligands: Syntheses and Molecular Structures of [Cp*MCl4(PH2R)] (M = Nb, Ta; Cp* = C5Me5;R = But, Ad, Cy, Ph, 2, 4, 6-Me3C6H2 (Mes))

Organometallic Niobium and Tantalum Complexes with Primary Phosphine Ligands: Syntheses and Molecular Structures of [Cp*MCl4(PH2R)] (M = Nb, Ta; Cp* = C5Me5;R = But, Ad, Cy, Ph, 2, 4, 6-Me3C6H2 (Mes))

Synthesis of Bis-Thiolato-Bridged Ru(III) Dimers. The Crystal Structure of [Ru(H2edta)(μ-SC6H5)]2

Synthesis and Structure of New (Polyphosphane)ruthenium Complexes with the Hemilabile Ligand 2‐(Diphenylphosphanyl)‐1‐methyl‐1H‐imidazole − An Unexpected Rearrangement of [RuCl2(PN)(PPh3)2]

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Organometallic Niobium and Tantalum Complexes with Primary Phosphine Ligands: Syntheses and Molecular Structures of [CpMCl4(PH2R)] (M = Nb, Ta; Cp = C5Me5;R = But, Ad, Cy, Ph, 2, 4, 6-Me3C6H2 (Mes))

Organometallic Niobium and Tantalum Complexes with Primary Phosphine Ligands: Syntheses and Molecular Structures of [CpMCl4(PH2R)] (M = Nb, Ta; Cp = C5Me5;R = But, Ad, Cy, Ph, 2, 4, 6-Me3C6H2 (Mes))

Synthesis of Bis-Thiolato-Bridged Ru(III) Dimers. The Crystal Structure of [Ru(H₂edta)(μ-SC₆H₅)]₂

Synthesis and Structure of New (Polyphosphane)ruthenium Complexes with the Hemilabile Ligand 2‐(Diphenylphosphanyl)‐1‐methyl‐1H‐imidazole − An Unexpected Rearrangement of [RuCl₂(PN)(PPh₃)₂]