The reaction of aryldiazonium salts with group VI arenemetal tricarbonyl derivatives

Connelly, Neil G.; Demidowicz, Zenon

doi:10.1016/s0022-328x(00)85647-8

Cited by 14 publications

(6 citation statements)

References 4 publications

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“…Of particular interest have been the relative ITaccepting abilities. In some studies it has been concluded that NO is a better IT-acceptor, whereas in others the reverse has been suggested (6)(7)(8)(9)(10)(11)(12)(13)(14).…”

Section: Introductionmentioning

confidence: 99%

Aryldiazenido complexes: structure, fluxionality, and properties of the iridium ethylene aryldiazenido complex [(η⁵-C₅Me₅)Ir(C₂H₄)(p-N₂C₆H₄OMe)][BF₄] and a comparison with the analogous nitrosyl complex [(η⁵-C₅Me₅)Ir(C₂H₄)(NO)][BF₄]

Yan¹,

Einstein²,

Sutton³

1995

Can. J. Chem.

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[Cp*Ir(C2H4)(N2Ar)][BF4] (1BF4; Ar = p-N2C6H4OMe) has been synthesized by reacting [ArN2] [BF4] with Cp*Ir(C2H4)2 at low temperature. An initial electrophilic attack of the incoming diazonium ion at iridium, followed by expulsion of C2H4, is postulated to account for the mild reaction conditions that are in sharp contrast to the usual inertness of the bis(ethylene) compound toward ligand substitution. The IR and nitrogen NMR data for 1BF4 and its 15Nα derivative unambiguously establish that the ArN2 ligand has the singly bent geometry in this complex in solution. The X-ray crystal structure confirms this for the solid state, and establishes that the plane of the aryldiazenido ligand is approximately perpendicular to the plane defined by the Ir atom and the centers of mass of the Cp* and ethylene ligands. An extended Hückel molecular orbital analysis of the singly bent aryldiazenido ligand has been carried out and satisfactorily accounts for the observed orientation of the ArN2 ligand. An analysis of the variable-temperature 1H and 13C NMR of 1BF4 indicates that both restricted rotation of the C2H4 ligand and a conformational isomerization of the aryldiazenido ligand are occurring, and ΔG≠270 for the ethylene rotation barrier is estimated at ≤ 51.5 ± 0.4 kJ mol−1. This is lower than the barrier of ΔG≠353 = 68.7 ± 0.2 kJ mol−1 determined previously for the analogous nitrosyl complex [Cp*Ir(C2H4)(NO)] [BF4] (2BF4) and it is suggested that in these half-sandwich complexes both NO and ArN2 function as single-faced π-acceptors, and in these circumstances ArN2 is the better π-acceptor. The ethylene in 1BF4 is readily displaced by PPh3 to give [Cp*Ir(PPh3)(N2Ar)][BF4] (3BF4). This reacts with NaBH4 to yield Cp*IrH(PPh3)(N2Ar) (4) in which the ArN2 ligand has switched to the doubly bent geometry, on the basis of the 15Nα NMR chemical shift data. Attempts to synthesize the corresponding chloro analogue 5 resulted in only the chloride salt of the singly bent ArN2 cation 3. For example, reaction of 3BF4 with HCl yields the aryldiazene complex [Cp*IrCl(PPh3)(NHNAr)] [BF4] (6), but deprotonation of this with Et3N yields 3Cl, not 5. Compound 1BF4 crystallized in the space group P21/n with a = 8.5780(10) Å, b = 20.5310(23) Å, c = 12.0310(15) Å, β = 93.500(10)°, and Z = 4. The structure was refined to Rf = 0.0281 on the basis of 2611 observed reflections with I°> 2.5σ(Io) in the range 2θ = 0–50° (Mo-Kα). Keywords: iridium, cyclopentadienyl, aryldiazenido, nitrosyl, ethylene.

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Section: Introductionmentioning

confidence: 99%

Aryldiazenido complexes: structure, fluxionality, and properties of the iridium ethylene aryldiazenido complex [(η⁵-C₅Me₅)Ir(C₂H₄)(p-N₂C₆H₄OMe)][BF₄] and a comparison with the analogous nitrosyl complex [(η⁵-C₅Me₅)Ir(C₂H₄)(NO)][BF₄]

Yan¹,

Einstein²,

Sutton³

1995

Can. J. Chem.

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“…Cl(5) 0.5969 (6) 0.1249 (4) 0.0611 (3) 0.0423 (11) 0.0228 (6) 0.0059 (2) -0.0097 (7) 0.0026 (4) -0.0015 (3) P(l) 0.26614 (13) 0.44867 (9) 0.18959 (8) 0.00429 (11) 0.00181 (5) 0.00167 (5) 0.00018 (6) 0.00018 (6) -0.00010 (4) P(2) -0.10113 (13) 0.51295 (8) 0.24408 (8) 0.00410 (11) 0.00160 (5) 0.00159 (5) 0.00004 (6) 0.00000 (6) -0.00006 ( 4)…”

Section: Nitrosylbis(l2-bis(diphenylphosphino)ethane)rhodium(2+)unclassified

“…In the osmium complex, which -0.122 0 C(xxl) is attached to P, and the atoms in the ring are sequentially numbered around the ring. 6 Isotropic thermal parameters of the phenyl hydrogen atoms are taken as the same as those of the respective carbon atoms to which they are bonded; the units are A2. c For RuCl3(NO)(PPh3)2.…”

Section: Nitrosylbis(l2-bis(diphenylphosphino)ethane)rhodium(2+)mentioning

confidence: 99%

“…For averaged quantities, the error is the larger of (1) an individual standard deviation or (2) the standard deviation of a single observation as calculated from the mean. 6 See ref 24. c may also be responsible for another apparent difference between the two structures: relative to our results, the atom N(l) is shifted in the previous structure determination away from Ru toward N(2) by about 0.013 Á, thus lengthening the Ru-N(l) distance and shortening the N(1)~N(2) distance.…”

Section: Moreover Whereas Mcardle Et Al Used the 2478 Data Havingmentioning

confidence: 99%

“…Several structures of (NO) 2(PPh3) aCPh^CeHs) complexes have been determined; M = Fe,1 Ru,2•3 Os,4 Co+,5 and Ir+. 6 Certain of these complexes have been found to be catalysts for the reaction7-10•11…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

Haymore¹,

Ibers²

1975

Inorg. Chem.

147

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From Diazonium Salts

Lane¹,

Pickett²,

Stanley³

1995

Inorganic Reactions and Methods

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The reaction of aryldiazonium salts with group VI arenemetal tricarbonyl derivatives

Cited by 14 publications

References 4 publications

Aryldiazenido complexes: structure, fluxionality, and properties of the iridium ethylene aryldiazenido complex [(η⁵-C₅Me₅)Ir(C₂H₄)(p-N₂C₆H₄OMe)][BF₄] and a comparison with the analogous nitrosyl complex [(η⁵-C₅Me₅)Ir(C₂H₄)(NO)][BF₄]

Aryldiazenido complexes: structure, fluxionality, and properties of the iridium ethylene aryldiazenido complex [(η⁵-C₅Me₅)Ir(C₂H₄)(p-N₂C₆H₄OMe)][BF₄] and a comparison with the analogous nitrosyl complex [(η⁵-C₅Me₅)Ir(C₂H₄)(NO)][BF₄]

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

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The reaction of aryldiazonium salts with group VI arenemetal tricarbonyl derivatives

Cited by 14 publications

References 4 publications

Aryldiazenido complexes: structure, fluxionality, and properties of the iridium ethylene aryldiazenido complex [(η5-C5Me5)Ir(C2H4)(p-N2C6H4OMe)][BF4] and a comparison with the analogous nitrosyl complex [(η5-C5Me5)Ir(C2H4)(NO)][BF4]

Aryldiazenido complexes: structure, fluxionality, and properties of the iridium ethylene aryldiazenido complex [(η5-C5Me5)Ir(C2H4)(p-N2C6H4OMe)][BF4] and a comparison with the analogous nitrosyl complex [(η5-C5Me5)Ir(C2H4)(NO)][BF4]

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

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Aryldiazenido complexes: structure, fluxionality, and properties of the iridium ethylene aryldiazenido complex [(η⁵-C₅Me₅)Ir(C₂H₄)(p-N₂C₆H₄OMe)][BF₄] and a comparison with the analogous nitrosyl complex [(η⁵-C₅Me₅)Ir(C₂H₄)(NO)][BF₄]

Aryldiazenido complexes: structure, fluxionality, and properties of the iridium ethylene aryldiazenido complex [(η⁵-C₅Me₅)Ir(C₂H₄)(p-N₂C₆H₄OMe)][BF₄] and a comparison with the analogous nitrosyl complex [(η⁵-C₅Me₅)Ir(C₂H₄)(NO)][BF₄]