Synthesis and structural characterisation of a ruthenium dinitrosyl complex with atrans-chelating bidentate diphosphine (1,10-bis(diphenylphosphinomethyl) [a] benzophenanthrene) chlorodi(nitrosyl)ruthenium tetrafluoroborate, [RuCl(NO)2{(Ph2PCH2)2-C18H10}]BF4

Mingos, D. Michael P.; Sherman, Darren J.; Williams, Ian D.

doi:10.1007/bf01023832

Cited by 8 publications

(9 citation statements)

References 10 publications

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“…Mingos and co-workers also studied complexes of the type trans-[Ru(L1a)Cl(NO) 2 ](BF 4 ). 87 They assigned this complex a square pyramidal geometry with the L1a ligand occupying trans-basal sites. While the structures of [RuCl(NO) 2 (PPh 3 ) 2 ] + and [OsCl(NO) 2 (PPh 3 ) 2 ] + approximate idealized square pyramidal and trigonal bipyramidal geometries, respectively, the P(1)-Ru-P(2) angle of trans-[Ru-(L1a)Cl(NO) 2 ] + (164.1(1)°) is closer to the angle expected for a square pyramidal complex.…”

Section: Preformed Trigonal Bipyramidal or Square Pyramidal Complexesmentioning

confidence: 99%

“…While the structures of [RuCl(NO) 2 (PPh 3 ) 2 ] + and [OsCl(NO) 2 (PPh 3 ) 2 ] + approximate idealized square pyramidal and trigonal bipyramidal geometries, respectively, the P(1)-Ru-P(2) angle of trans-[Ru-(L1a)Cl(NO) 2 ] + (164.1(1)°) is closer to the angle expected for a square pyramidal complex. 87 In the [RuCl(NO) 2 (PPh 3 ) 2 ] + complex, one of the nitrosyl ligands is strongly bent while the other is linear, for the [OsCl(NO) 2 (PPh 3 ) 2 ] + complex both nitrosyl ligands are approximately linear, and in the trans-[Ru(L1a)-Cl(NO) 2 ] + complex one nitrosyl ligand is partially bent (156.2(7)°) while the other is approximately linear (172.5(6)°). The 1 H NMR spectroscopy of the trans-[Ru(L1a)Cl(NO) 2 ](BF 4 ) complex demonstrates inequivalent -CH 2 -resonances implying that in either the square pyramidal or trigonal bipyramidal structure the two protons on the methylene group remain in different chemical environments.…”

Section: Preformed Trigonal Bipyramidal or Square Pyramidal Complexesmentioning

confidence: 99%

See 1 more Smart Citation

Transition-Metal Complexes Containing trans-Spanning Diphosphine Ligands

and¹,

Aggarwal²,

Marschilok³

et al. 2001

Chem. Rev.

144

108

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Section: Preformed Trigonal Bipyramidal or Square Pyramidal Complexesmentioning

confidence: 99%

Section: Preformed Trigonal Bipyramidal or Square Pyramidal Complexesmentioning

confidence: 99%

Transition-Metal Complexes Containing trans-Spanning Diphosphine Ligands

and¹,

Aggarwal²,

Marschilok³

et al. 2001

Chem. Rev.

144

108

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“…On one hand the nitrosyl adducts of both heme and nonheme iron enzymes have recognized biological functions ranging from signal transduction by soluble guanylyl cyclase, sGC, to the regulation of gene transcription by the soxRS -mediated oxidative-stress response and of these complexes, the cationic cis -dinitrosyl complex [RuCl(NO) 2 (PPh 3 ) 2 ] + , with both bent and linear nitrosyls, is an archetype for the relationship of MNO binding geometry to the metal's electronic structure and fluxionality. − Because of the critical biological roles of the NO/heme interaction, there is a resurgence of interest in the chemistry of iron porphyrin nitrosyls − and this has in turn rekindled interest in the corresponding ruthenium analogues.…”

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confidence: 99%

Synthesis and Axial Ligand Substitution Chemistry of Ru(TTP)(NO)X. Structures of Ru(TTP)(NO)X (X = ONO, OH)

1998

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New complexes of the family Ru(TTP)(NO)X, where TTP = tetra-p-tolylporphyrinato dianion, and X = OMe, Cl, OH, SH, S-p-tolyl, O2CH, ONO, ONO2, N3, or NCS, have been prepared by a variety of high-yield metathesis techniques from Ru(TTP)(CO)(MeOH). New complexes have been characterized by IR, NMR, and UV spectroscopies as well as by cyclic voltammetry, elemental analysis, and, in two cases, by X-ray crystallography. The two complexes which have been characterized by single-crystal X-ray diffraction, the hydroxide and nitrite complexes 6 and 10 both crystallize in the monoclinic space group P21/n and have Z = 6, with two independent metalloporphyrins in the unit cell, one (ordered) lying on a general position and the other (disordered) with the ruthenium on an inversion center. Acid labilization of the methoxide results in facile substitution kinetics at room temperature and with the exception of the sulfhydryl complex, L = SH, the resulting complexes are air stable and thermally robust species. For example, the formate derivative cannot be decarboxylated thermally or photolytically to give a hydrido complex, and the azido complex does not eliminate dinitrogen under similar conditions to give a nitrido complex.

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“…In the next step (iii), the respective {RuNO} n 15 NO couple. 15,[17][18][19] The "X [20][21][22] Ru-N-O angles are given for the bent RuNO moiety.…”

Section: Synthesismentioning

confidence: 99%

“…Fig.2Known {Ru(NO) 2 } 8 dinitrosyls (charges are drawn at the central metal atom); several publications deal with salts of A, including a tetrafluoridoborate with a 14 NO/15 NO couple 15,[17][18][19]. The "X" in [C]X is [Ru(NO)(OH)(NO 2 ) 2 Cl 2 ] [20][21][22]. Ru-N-O angles are given for the bent RuNO moiety.…”

mentioning

confidence: 99%

NO-binding in {Ru(NO)₂}⁸-type [Ru(NO)₂(PR₃)₂X]BF₄ compounds

Gallien¹,

Schaniel

Woike

et al. 2014

Dalton Trans.

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Two different structure types were found for a series of mononuclear dinitrosyl complexes of the general formula [RuL2(NO)2X]BF4 (L = monodentate phosphane, X = Cl, Br, I). The {Ru(NO)2}(8)-type target compounds were prepared by the reduction of the respective {RuNO}(6) precursors and subsequent oxidative addition of (NO)BF4. About one half of the new compounds share their molecular structure with the hitherto only representative of this class of dinitrosyls, Pierpont and Eisenberg's [RuCl(NO)2(PPh3)2]PF6·C6H6 (Inorg. Chem., 1972, 11, 1088-1094). The Cs-symmetric cations exhibit both a linear and a bent Ru-N-O fragment, in line with a formal 6 + 2 split of the {Ru(NO)2}(8) electron sum in the sense of a [Ru(II)(NO(+))((1)NO(-))](2+) bonding. The coordination entity's configuration in this subgroup is described by IUPAC's polyhedral symbol SPY-5. Continuous shape measures (CShM) as defined by Alvarez et al. (Coord. Chem. Rev., 2005, 249, 1693-1708) reveal a uniform deviation from the L-M-L angles expected for SPY-5, in a narrower sense, towards a vacant octahedron (vOC-5). DFT calculations confirmed that Enemark and Feltham's analysis (Coord. Chem. Rev., 1974, 13, 339-406) of the electronic situation of the {Ru(NO)2}(8) group remains adequate. The same holds for the second subclass of new compounds the existence of which had been predicted in the same paper by Enemark and Feltham, namely C(2v)-symmetric, TBPY-5-type cations with two almost equally bonded nitrosyl ligands. In agreement with an 8 + 0 distribution of the relevant electrons, the formal [Ru(0)(NO(+))2](2+) entities are found for L/X couples that donate more electron density on the central metal. Two solid compounds (8a/b, 12a/b) were found in both structures including the special case of the P(i)Pr3/Br couple 12a/b, which led to crystals that contained both structure types in the same solid. Conversely, four compounds showed a single form in the solid but both forms in dichloromethane solution in terms of the solutions' IR spectra. The irradiation of crystalline 12 with blue laser light resulted in the photoisomerisation of, mainly, the bent (1)NO(-) ligand in terms of low-temperature IR spectroscopy.

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Synthesis and structural characterisation of a ruthenium dinitrosyl complex with atrans-chelating bidentate diphosphine (1,10-bis(diphenylphosphinomethyl) [a] benzophenanthrene) chlorodi(nitrosyl)ruthenium tetrafluoroborate, [RuCl(NO)2{(Ph2PCH2)2-C18H10}]BF4

Cited by 8 publications

References 10 publications

Transition-Metal Complexes Containing trans-Spanning Diphosphine Ligands

Transition-Metal Complexes Containing trans-Spanning Diphosphine Ligands

Synthesis and Axial Ligand Substitution Chemistry of Ru(TTP)(NO)X. Structures of Ru(TTP)(NO)X (X = ONO, OH)

NO-binding in {Ru(NO)₂}⁸-type [Ru(NO)₂(PR₃)₂X]BF₄ compounds

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Synthesis and structural characterisation of a ruthenium dinitrosyl complex with atrans-chelating bidentate diphosphine (1,10-bis(diphenylphosphinomethyl) [a] benzophenanthrene) chlorodi(nitrosyl)ruthenium tetrafluoroborate, [RuCl(NO)2{(Ph2PCH2)2-C18H10}]BF4

Cited by 8 publications

References 10 publications

Transition-Metal Complexes Containing trans-Spanning Diphosphine Ligands

Transition-Metal Complexes Containing trans-Spanning Diphosphine Ligands

Synthesis and Axial Ligand Substitution Chemistry of Ru(TTP)(NO)X. Structures of Ru(TTP)(NO)X (X = ONO, OH)

NO-binding in {Ru(NO)2}8-type [Ru(NO)2(PR3)2X]BF4 compounds

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NO-binding in {Ru(NO)₂}⁸-type [Ru(NO)₂(PR₃)₂X]BF₄ compounds