Five‐ and Six‐Coordinate Ruthenium(<scp>II</scp>) Complexes Containing the Bidentate Phosphane (−)‐N,N‐Bis(diphenylphosphanyl)‐(S)‐1‐phenylethylamine [(S)‐peap]: X‐ray Crystal Structure of the First 16‐Electron Ruthenium Complex Bearing a Four‐Membered Ring [RuCl{κ2‐P,P‐(S)‐peap}2][SbF6]·C2H4Cl2

Dı́ez, Josefina; Gamasa, M. Pilar; Gimeno, José; Rodríguez, Yolanda; García-Granda, Santiago

doi:10.1002/ejic.200300755

Cited by 10 publications

(3 citation statements)

References 36 publications

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“…The latter present in all cases much smaller degrees of unsymmetry (Δd ≤ 0.08 Å) than the high-spin ones (0.07 ≤ Δd ≤ 1.14 Å), with the only exception of a Ru complex, 29 in the region of short M−P distances and slightly overlapping with the region of the calculated values for the high-spin Fe complexes, probably due to steric encumbrance of their two DPPA ligands.…”

Section: Inorganic Chemistrymentioning

confidence: 87%

Unsymmetrical Chelation of N-Thioether-Functionalized Bis(diphenylphosphino)amine-Type Ligands and Substituent Effects on the Nuclearity of Iron(II) Complexes: Structures, Magnetism, and Bonding

et al. 2015

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Starting from the short-bite ligands N-thioether-functionalized bis(diphenylphosphino)amine-type (Ph2P)2N(CH2)3SMe (1) and (Ph2P)2N(p-C6H4)SMe (2), the Fe(II) complexes [FeCl2(1)]n (3), [FeCl2(2)]2 (4), [Fe(OAc)(1)2]PF6 (5), and [Fe(OAc)(2)2]PF6 (6) were synthesized and characterized by Fourier transform IR, mass spectrometry, elemental analysis, and also by X-ray diffraction for 3, 4, and 6. Complex 3 is a coordination polymer in which 1 acts as a P,P-pseudochelate and a (P,P),S-bridge, whereas 4 has a chlorido-bridged dinuclear structure in which 2 acts only as a P,P-pseudochelate. Since these complexes were obtained under strictly similar synthetic and crystallization conditions, these unexpected differences were ascribed to the different spacer between the nitrogen atom and the −SMe group. In both compounds, one Fe–P bond was found to be unusually long, and a theoretical analysis was performed to unravel the electronic or steric reasons for this difference. Density functional theory calculations were performed for a set of complexes of general formula [FeCl2(SR2){R21PN(R2)P′R23}] (R = H, Me; R1, R2, and R3 = H, Me, Ph), to understand the reasons for the significant deviation of the iron coordination sphere away from tetrahedral as well as from trigonal bipyramidal and the varying degree of unsymmetry of the two Fe–P bonds involving pseudochelating PN(R)P ligands. Electronic factors nicely explain the observed structures, and steric reasons were further ruled out by the structural analysis in the solid-state of the bis-chelated complex 6, which displays usual and equivalent Fe–P bond lengths. Magnetic susceptibility studies were performed to examine how the structural differences between 3 and 4 would affect the interactions between the iron centers, and it was concluded that 3 behaves as an isolated high-spin Fe(II) mononuclear complex, while significant intra- and intermolecular ferromagnetic interactions were evidenced for 4 at low temperatures. Complexes 3 and 4 were also tested in catalytic ethylene oligomerization but did not exhibit any significant activity under the studied conditions.

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Section: Inorganic Chemistrymentioning

confidence: 87%

Unsymmetrical Chelation of N-Thioether-Functionalized Bis(diphenylphosphino)amine-Type Ligands and Substituent Effects on the Nuclearity of Iron(II) Complexes: Structures, Magnetism, and Bonding

et al. 2015

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“…28 This year also includes the first reported 16-electron ruthenium complex containing two four-membered rings, [RuCl{k 2 -P,P-(S)-(P(Ph) 2 N(CHMePh)P(Ph 2 )}][SbF 6 ]. 29 New Ru(II) mononitrosyl complexes [Ru(NO)LCl 2 ], [Ru(NO)L(en)]Cl 2 and [Ru(NO)(L) 2 ]Cl [L = the potentially N,N,O-donor ligand bis (3,5-dimethlypyrazol-1yl)methan-sulfonate or bis (3,5-dimethlypyrazol-1yl)acetate] have been isolated; in the [Ru(NO)(L) 2 ]Cl complexes one O-donor of L is free and one is bound, with the two undergoing 'on-off' interconversion as shown by NMR spectroscopy. 30 The coordination chemistry of azpy has attracted much attention over the year.…”

Section: Coordination Complexesmentioning

confidence: 99%

15 Noble metals

Fletcher¹

2005

Annu. Rep. Prog. Chem., Sect. A

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A few exceptional publications have demonstrated new versatility in the chemistry of the noble metals over the last year. These include the highly luminescent hybrid pyridyl-carbene complexes of Ru(II) published by Son et al. (Inorg. Chem., 2004, 43, 6896) and the palladium and ruthenium complexes of the diimine ''heterosuperbenzene'' ligand of Draper and coworkers (J. Am. Chem. Soc., 2004, 126, 8694). The care and attention of Yang et al. (Chem. Commun., 2004, 2232 in the detailed study of the effects of isomerism in the luminescent properties of cyclometallated 2-phenylpyridine iridium(III) complexes is particularly noteworthy, as is the isolation of long chains composed of platinum species bridged with octadiynyl ligands as described by Zeng et al. (Organometallics, 2004, 23, 5896) which offers new insights into the preparation of electron rich molecular wires. Finally, the unexpected oxidative carbon-carbon bond cleavage in the formation of silver N-heterocyclic carbene complexes reported by Crabtree and co-workers (Chem. Commun., 2004, 2176) is worth emphasizing.

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“…Polydentate ligands containing phosphorus and nitrogen atoms have been widely used to obtain chelate complexes in coordination chemistry − and in relation with homogeneous catalysis. − In particular bis(phosphino)diamines prepared from enantiopures 1,2-diamines have been used like auxiliary ligands in applications of organometallic catalysis for stereoselective organic transformations, like asymmetric hydrogenation reactions, − asymmetric hydroboration, Diels−Alder catalysis, etc.…”

Section: Introductionmentioning

confidence: 99%

Coordinatively Unsaturated Semisandwich Complexes of Ruthenium with Phosphinoamine Ligands and Related Species: A Complex Containing (R,R)-1,2-Bis((diisopropylphosphino)amino)cyclohexane in a New Coordination Form κ³P,P‘,N-η²-P,N

et al. 2007

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The syntheses of the chloro complexes [Ru(eta5-C5R5)Cl(L)] (R = H, Me; L = phosphinoamine ligand) (1a-d) have been carried out by reaction of [(eta5-C5H5)RuCl(PPh3)2] or {(eta5-C5Me5)RuCl}4 with the corresponding phosphinoamine (R,R)-1,2-bis((diisopropylphosphino)amino)cyclohexane), R,R-dippach, or 1,2-bis(((diisopropylphosphino)amino)ethane), dippae. The chloride abstraction reactions from these compounds lead to different products depending on the starting chlorocomplex and the reaction conditions. Under argon atmosphere, chloride abstraction from [(eta5-C5Me5)RuCl(R,R-dippach)] with NaBAr'4 yields the compound [(eta5-C5Me5)Ru(kappa3P,P'-(R,R)-dippach)][BAr'4] (2b) which exhibits a three-membered ring Ru-N-P by a new coordination form of this phosphinoamine. However, under the same conditions the reaction starting from [(eta5-C5Me5)RuCl(dippae)] yields the unsaturated 16 electron complex [(eta5-C5Me5)Ru(dippae)][BAr'4] (2d). The bonding modes of R,R-dippach and dippae ligands have been analyzed by DFT calculations. The possibility of tridentate P,N,P-coordination of the phosphinoamide ligand to a fragment [(eta5-C5Me5)Ru]+ is always present, but only the presence of a cyclohexane unit in the ligand framework converts this bonding mode in a more favorable option than the usual P,P-coordination. Dinitrogen [(eta5-C5R5)Ru(N2)(L)][BAr'4] (3a-d) and dioxygen complexes [(eta5-C5H5)Ru(O2)(R,R-dippach)][BPh4] (4a) and [(eta5-C5Me5)Ru(O2)(L)][BPh4] (4b,d) have been prepared by chloride abstraction under dinitrogen or dioxygen atmosphere, respectively. The presence of 16 electron [(eta5-C5H5)Ru(R,R-dippach)]+ species in fluorobenzene solutions of the corresponding dinitrogen or dioxygen complexes in conjunction with the presence of [BAr'4]- gave in some cases a small fraction of [Ru(eta5-C5H5)(eta6-C6H5F)][BAr'4] (5a), which has been isolated and characterized by X-ray diffraction.

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Cited by 10 publications

References 36 publications

Unsymmetrical Chelation of N-Thioether-Functionalized Bis(diphenylphosphino)amine-Type Ligands and Substituent Effects on the Nuclearity of Iron(II) Complexes: Structures, Magnetism, and Bonding

Unsymmetrical Chelation of N-Thioether-Functionalized Bis(diphenylphosphino)amine-Type Ligands and Substituent Effects on the Nuclearity of Iron(II) Complexes: Structures, Magnetism, and Bonding

15 Noble metals

Coordinatively Unsaturated Semisandwich Complexes of Ruthenium with Phosphinoamine Ligands and Related Species: A Complex Containing (R,R)-1,2-Bis((diisopropylphosphino)amino)cyclohexane in a New Coordination Form κ³P,P‘,N-η²-P,N

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Cited by 10 publications

References 36 publications

Unsymmetrical Chelation of N-Thioether-Functionalized Bis(diphenylphosphino)amine-Type Ligands and Substituent Effects on the Nuclearity of Iron(II) Complexes: Structures, Magnetism, and Bonding

Unsymmetrical Chelation of N-Thioether-Functionalized Bis(diphenylphosphino)amine-Type Ligands and Substituent Effects on the Nuclearity of Iron(II) Complexes: Structures, Magnetism, and Bonding

15 Noble metals

Coordinatively Unsaturated Semisandwich Complexes of Ruthenium with Phosphinoamine Ligands and Related Species: A Complex Containing (R,R)-1,2-Bis((diisopropylphosphino)amino)cyclohexane in a New Coordination Form κ3P,P‘,N-η2-P,N

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Coordinatively Unsaturated Semisandwich Complexes of Ruthenium with Phosphinoamine Ligands and Related Species: A Complex Containing (R,R)-1,2-Bis((diisopropylphosphino)amino)cyclohexane in a New Coordination Form κ³P,P‘,N-η²-P,N