Comparison of linear nitrosyl and singly bent aryldiazo complexes of ruthenium.  Structures of trichloronitrosylbis(triphenylphosphine)ruthenium, RuCl3(NO)(P(C6H5)3)2, and trichloro(p-tolyl)diazobis(triphenylphosphine)ruthenium-dichloromethane, RuCl3(p-NNC6H4CH3)(P(C6H5)3)2.CH2Cl2

Haymore, Barry L.; Ibers, James A.

doi:10.1021/ic50154a041

Cited by 147 publications

(13 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…a singly-bent or a double-bent geometry. The 1594−1576 cm -1 frequency represents, in fact, a borderline case also for the empirical rule proposed by Haymore and Ibers for which the observed and corrected νNN frequencies fall into at least two groups, those above and below 1550−1530 cm -1 , with those above characteristic of a singly-bent aryldiazenido ligand. In fact, if we hypothesize the presence of a singly-bent ArN 2 + ligand bonded to a formal Mn(1−) d 8 central metal, the observed pentacoordination results as being plausible and the complex may be compared with related iron(0) [Fe(CO) 2 (PPh 3 ) 2 (C 6 H 5 N 2 )]BF 4 29a and [Fe(ArN 2 )P 4 ]BPh 4 4b [P = P(OEt) 3 , PPh(OEt) 2 ] or cobalt(I) [Co(ArN 2 )P 4 ](BPh 4 ) 2 derivatives which show, however, a higher νN 2 frequency [1660−1760 cm -1 for Fe(0) and 1770−1790 cm -1 for Co(I)] than our compounds 5 − 7 .…”

Section: Resultsmentioning

confidence: 70%

Aryldiazene, Aryldiazenido, and Hydrazine Complexes of Manganese. Preparation, Characterization, and X-ray Crystal Structures of [Mn(CO)₃(4-CH₃C₆H₄NNH){PPh(OEt)₂}₂]BF₄ and [Mn(CO)₃(NH₂NH₂){PPh(OEt)₂}₂]BPh₄ Derivatives

Albertin¹,

Antoniutti²,

Bacchi³

et al. 1997

Inorg. Chem.

View full text Add to dashboard Cite

Aryldiazene complexes [Mn(CO)(3)(ArN=NH)P(2)]BF(4) (1, 2) and [{Mn(CO)(3)P(2)}(2)(&mgr;-HN=NArArN=NH)](BF(4))(2) (3, 4) [P = PPh(OEt)(2), PPh(2)OEt; Ar = C(6)H(5), 2-CH(3)C(6)H(4), 4-CH(3)C(6)H(4), 4-CH(3)OC(6)H(4); ArAr = 4,4'-C(6)H(4)C(6)H(4), 4,4'-(2-CH(3))C(6)H(3)C(6)H(3)(2-CH(3)), 4,4'-C(6)H(4)CH(2)C(6)H(4)] were prepared by reacting hydride species MnH(CO)(3)P(2) with the appropriate aryldiazonium cations in CH(2)Cl(2) or acetone solutions at -80 degrees C. The compounds were characterized by IR, (1)H and (31)P NMR spectra (with (15)N isotopic substitution), and a single-crystal X-ray structure determination. The complex [Mn(CO)(3)(4-CH(3)C(6)H(4)N=NH){PPh(OEt)(2)}(2)]BF(4) (1c) crystallizes in the space group C2/c with a = 31.857(5) Å, b = 11.119(2) Å, c = 22.414(3) Å, beta = 97.82(1) degrees, and Z = 8. Treatment of aryldiazene compounds 1-4 with NEt(3) gave the pentacoordinate aryldiazenido [Mn(CO)(2)(ArN(2))P(2)] (5, 6) and [{Mn(CO)(2)P(2)}(2)(&mgr;-N(2)ArArN(2))] (7, 8) [P = PPh(OEt)(2), PPh(2)OEt; Ar = C(6)H(5), 4-CH(3)C(6)H(4); ArAr = 4,4'-C(6)H(4)C(6)H(4), 4,4'-(2-CH(3))C(6)H(3)C(6)H(3)(2-CH(3))] derivatives. Protonation reactions of these aryldiazenido complexes 5-8 with HCl afforded the aryldiazene [MnCl(CO)(2)(ArN=NH)P(2)] (9) and [{MnCl(CO)(2)P(2)}(2)(&mgr;-HN=NArArN=NH)] (10) derivatives. Hydrazine complexes [Mn(CO)(3)(RNHNH(2))P(2)]BPh(4) (11, 12) [P = PPh(OEt)(2), PPh(2)OEt; R = H, CH(3), C(6)H(5), 4-NO(2)C(6)H(4)] were prepared by allowing hydride species MnH(CO)(3)P(2) to react first with triflic acid and then with the appropriate hydrazine. Their characterization by IR, (1)H and (31)P NMR spectra, and an X-ray crystal structure determination is reported. The compound [Mn(CO)(3)(NH(2)NH(2)){PPh(OEt)(2)}(2)]BPh(4) (11a) crystallizes in the space group P&onemacr; with a = 13.772(3) Å, b = 14.951(4) Å, c = 13.319(3) Å, alpha = 104.47(1) degrees, beta = 100.32(1) degrees, gamma = 111.08(1) degrees, and Z = 2. Oxidation reactions of hydrazine compounds 11 and 12 with Pb(OAc)(4) at -40 degrees C gave stable aryldiazene [Mn(CO)(3)(RN=NH)P(2)]BPh(4) and thermally unstable (upon reaching -40 degrees C) diazene [Mn(CO)(3)(HN=NH)P(2)]BPh(4) derivatives.

show abstract

Section: Resultsmentioning

confidence: 70%

Aryldiazene, Aryldiazenido, and Hydrazine Complexes of Manganese. Preparation, Characterization, and X-ray Crystal Structures of [Mn(CO)₃(4-CH₃C₆H₄NNH){PPh(OEt)₂}₂]BF₄ and [Mn(CO)₃(NH₂NH₂){PPh(OEt)₂}₂]BPh₄ Derivatives

Albertin¹,

Antoniutti²,

Bacchi³

et al. 1997

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

“…The physical properties of the {FeNO} 7 centers in 1b are comparable to those of similar mononuclear non-heme iron complexes. The ν NO value of 1785 cm -1 observed in the IR spectrum falls in the expected range for 18-electron octahedral complexes, after applying the correction for charge and considering the position of Fe in the periodic table . The presence of only one NO stretch indicates the absence of significant vibrational coupling between the two {FeNO} 7 centers, which would produce symmetric and asymmetric stretching modes which are infrared active in a complex of C s symmetry.…”

Section: Discussionmentioning

confidence: 68%

A Carboxylate-Bridged Non-Heme Diiron Dinitrosyl Complex

1996

View full text Add to dashboard Cite

The reaction of nitric oxide with the carboxylate-bridged diiron(II) complex [Fe(2)(Et-HPTB)(O(2)CPh)](BF(4))(2) (1a) afforded the dinitrosyl adduct, [Fe(2)(NO)(2)(Et-HPTB)(O(2)CPh)](BF(4))(2) (1b), where Et-HPTB = N,N,N',N'-tetrakis(N-ethyl-2-benzimidazolylmethyl)-2-hydroxy-1,3-diaminopropane, in 69% yield. Compound 1b further reacts with dioxygen to form the bis(nitrato) complex, [Fe(2)(Et-HPTB)(NO(3))(2)(OH)](BF(4))(2) (1c). The structure of 1b was determined by X-ray crystallography (triclinic, P&onemacr;, a = 13.5765(8) Å, b = 15.4088(10) Å, c = 16.2145(10) Å, alpha = 73.656(1) degrees, beta = 73.546(1) degrees, gamma = 73.499(1) degrees, V = 3043.8(7) Å(3), T = -80 degrees C, Z = 2, and R = 0.085 and R(w) = 0.095 for 5644 independent reflections with I > 3sigma(I)). The two nitrosyl units are equivalent with an average Fe-N-O angle of 167.4 +/- 0.8 degrees. Spectroscopic characterization of solid 1b revealed an NO stretch at 1785 cm(-)(1) in the infrared and Mössbauer parameters of delta = 0.67 mm s(-)(1) and DeltaE(Q) = 1.44 mm s(-)(1) at 4.2 K. These data are comparable to those for other {FeNO}(7) systems. An S = (3)/(2) spin state was assigned from magnetic susceptibility studies to the two individual {FeNO} centers, each of which has a nitrosyl ligand antiferromagnetically coupled to iron. A least-squares fit of the chi vs temperature plots to a theoretical model yielded an exchange coupling constant J of -23 cm(-)(1), where H = -2JS(1).S(2), indicating that the two S = (3)/(2) centers are antiferromagnetically coupled to one another. An extended Hückel calculation on a model complex, [Fe(2)(NO)(2)(NH(3))(6)(O(2)CH)(OH)](2+), revealed that the magnitudes of Fe-N-O angles are dictated by pi-bonding interactions between the Fe d(xz)() and NO pi orbitals.

show abstract

“…The ν(NN) band of the aryldiazenido ligand is also present in the 1779−1720 cm -1 region and is shifted to lower frequencies (about 35 cm -1 ) in the labeled ArN⋮ 15 N compound, according to the proposed assignment. These values for the N−N stretching frequency are indicative of a singly bent aryldiazenido ligand, and this statement was shown to be correct by X-ray structure determination of 5b , discussed below. The 15 N NMR spectra also fit the presence of a singly bent ArN 2 ligand, , showing a triplet at 19.7 ppm ( 2 J 15 N 31 P = 20 Hz) due to coupling with two magnetically equivalent phosphorus nuclei for the [Fe(C 6 H 5 N⋮ 15 N)(CO) 2 {P(OEt) 3 } 2 ]BPh 4 ( 1a 1 ) derivative.…”

Section: Resultsmentioning

confidence: 82%

Reactivity of Hydrides FeH₂(CO)₂P₂(P = Phosphites) with Aryldiazonium Cations: Preparation, Characterization, X-ray Crystal Structure, and Electrochemical Studies of Mono- and Binuclear Aryldiazenido Complexes

et al. 1998

View full text Add to dashboard Cite

Mono- and binuclear aryldiazenido complexes [Fe(ArN(2))(CO)(2)P(2)]BPh(4) (1-4) and [{Fe(CO)(2)P(2)}(2)(&mgr;-N(2)Ar-ArN(2))](BPh(4))(2) (5-8) [P = P(OEt)(3), PPh(OEt)(2), PPh(2)OEt, P(OPh)(3); Ar = C(6)H(5), 2-CH(3)C(6)H(4), 4-CH(3)C(6)H(4); Ar-Ar = 4,4'-C(6)H(4)-C(6)H(4), 4,4'-(2-CH(3))C(6)H(3)-C(6)H(3)(2-CH(3)), 4,4'-C(6)H(4)-CH(2)-C(6)H(4)] were prepared by allowing hydride species FeH(2)(CO)(2)P(2) to react with an excess of mono- (ArN(2))(BF(4)) or bis-aryldiazonium (N(2)Ar-ArN(2))(BF(4))(2) salts, respectively, at low temperature. A reaction path involving a hydride-aryldiazene intermediate [FeH(ArN=NH)(CO)(2)P(2)](+), which, through the loss of H(2), affords the final aryldiazenido complexes 1-8, is proposed. The compounds were characterized by (1)H and (31)P{(1)H} NMR spectroscopy (including (15)N isotopic substitution) and X-ray crystal structure determination. The complex [Fe(CO)(2){P(OEt)(3)}(2){&mgr;-4,4'-N(2)(2-CH(3))C(6)H(3)-C(6)H(3)(2-CH(3))N(2)}](BPh(4))(2) (5b) crystallizes in the space group P&onemacr; with a = 15.008(4) Å, b = 17.094(5) Å, c = 10.553(3) Å, alpha = 99.56(1) degrees, beta = 102.80(1) degrees, gamma = 65.30(1) degrees, and Z = 1. The structure is centrosymmetric and consists of binuclear cations with the two iron atoms in a quite regular trigonal bipyramidal environment, with the two CO in the equatorial and the two phosphites in the apical position, respectively. Aryldiazenido complexes 1-8 react with strong acids HX (X = Cl, CF(3)SO(3), CF(3)CO(2)) to give the corresponding aryldiazene derivatives, according to the equilibrium [Fe(ArN(2))(CO)(2)P(2)](+) + HX right harpoon over left harpoon [FeX(ArN=NH)(CO)(2)P(2)](+). Electrochemical studies of both mono- (1-4) and binuclear (5-8) compounds were undertaken, and a mechanism for oxidation and reduction processes is proposed.

show abstract

Comparison of linear nitrosyl and singly bent aryldiazo complexes of ruthenium. Structures of trichloronitrosylbis(triphenylphosphine)ruthenium, RuCl3(NO)(P(C6H5)3)2, and trichloro(p-tolyl)diazobis(triphenylphosphine)ruthenium-dichloromethane, RuCl3(p-NNC6H4CH3)(P(C6H5)3)2.CH2Cl2

Cited by 147 publications

References 16 publications

Aryldiazene, Aryldiazenido, and Hydrazine Complexes of Manganese. Preparation, Characterization, and X-ray Crystal Structures of [Mn(CO)₃(4-CH₃C₆H₄NNH){PPh(OEt)₂}₂]BF₄ and [Mn(CO)₃(NH₂NH₂){PPh(OEt)₂}₂]BPh₄ Derivatives

Aryldiazene, Aryldiazenido, and Hydrazine Complexes of Manganese. Preparation, Characterization, and X-ray Crystal Structures of [Mn(CO)₃(4-CH₃C₆H₄NNH){PPh(OEt)₂}₂]BF₄ and [Mn(CO)₃(NH₂NH₂){PPh(OEt)₂}₂]BPh₄ Derivatives

A Carboxylate-Bridged Non-Heme Diiron Dinitrosyl Complex

Reactivity of Hydrides FeH₂(CO)₂P₂(P = Phosphites) with Aryldiazonium Cations: Preparation, Characterization, X-ray Crystal Structure, and Electrochemical Studies of Mono- and Binuclear Aryldiazenido Complexes

Contact Info

Product

Resources

About

Comparison of linear nitrosyl and singly bent aryldiazo complexes of ruthenium. Structures of trichloronitrosylbis(triphenylphosphine)ruthenium, RuCl3(NO)(P(C6H5)3)2, and trichloro(p-tolyl)diazobis(triphenylphosphine)ruthenium-dichloromethane, RuCl3(p-NNC6H4CH3)(P(C6H5)3)2.CH2Cl2

Cited by 147 publications

References 16 publications

Aryldiazene, Aryldiazenido, and Hydrazine Complexes of Manganese. Preparation, Characterization, and X-ray Crystal Structures of [Mn(CO)3(4-CH3C6H4NNH){PPh(OEt)2}2]BF4 and [Mn(CO)3(NH2NH2){PPh(OEt)2}2]BPh4 Derivatives

Aryldiazene, Aryldiazenido, and Hydrazine Complexes of Manganese. Preparation, Characterization, and X-ray Crystal Structures of [Mn(CO)3(4-CH3C6H4NNH){PPh(OEt)2}2]BF4 and [Mn(CO)3(NH2NH2){PPh(OEt)2}2]BPh4 Derivatives

A Carboxylate-Bridged Non-Heme Diiron Dinitrosyl Complex

Reactivity of Hydrides FeH2(CO)2P2(P = Phosphites) with Aryldiazonium Cations: Preparation, Characterization, X-ray Crystal Structure, and Electrochemical Studies of Mono- and Binuclear Aryldiazenido Complexes

Contact Info

Product

Resources

About

Aryldiazene, Aryldiazenido, and Hydrazine Complexes of Manganese. Preparation, Characterization, and X-ray Crystal Structures of [Mn(CO)₃(4-CH₃C₆H₄NNH){PPh(OEt)₂}₂]BF₄ and [Mn(CO)₃(NH₂NH₂){PPh(OEt)₂}₂]BPh₄ Derivatives

Aryldiazene, Aryldiazenido, and Hydrazine Complexes of Manganese. Preparation, Characterization, and X-ray Crystal Structures of [Mn(CO)₃(4-CH₃C₆H₄NNH){PPh(OEt)₂}₂]BF₄ and [Mn(CO)₃(NH₂NH₂){PPh(OEt)₂}₂]BPh₄ Derivatives

Reactivity of Hydrides FeH₂(CO)₂P₂(P = Phosphites) with Aryldiazonium Cations: Preparation, Characterization, X-ray Crystal Structure, and Electrochemical Studies of Mono- and Binuclear Aryldiazenido Complexes