The formation of amine and amide complexes in the reactions between [Mo(NO){HB(3,5-Me2C3N2H)3}X2] (X = Cl or I) and saturated cyclic amines. The molecular structures of [Mo(NO){HB(3,5-Me2C3N2H)3}I(NHC5H10)] and [Mo(NO){HB(3,5-Me2C3N2H)3}I(NC4H8)]

Alobaidi, Najat; Hamor, T. A.; Jones, Christopher J.; McCleverty, Jon A.; Paxton, Keith; Howes, Andrew; Hursthouse, Michael B.

doi:10.1016/s0277-5387(00)80707-x

Cited by 17 publications

(11 citation statements)

References 11 publications

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“…This has been attributed ' to the trans influence of the strongly n-accepting nitrosyl ligand. The short Mo-N(nitrosy1) length, 1.786 (7) A, is also in good agreement with previous results and is consistent with a strong bonding interaction. The Mo-N(pyrazoly1) bond trans to the iodo substituent is the shortest of these, reflecting the lack of significant n interaction between the halogen and the metal.…”

Section: 750( 1) N( 1 )-O( 1) 1142( 8)supporting

confidence: 91%

Synthesis and electrochemistry of [{Mo(NO)[HB(3,5-Me2C3HN2)3]Cl}2{1,2-(NH)2C6H4}] and the crystal structure of [{Mo(NO)[HB(3,5-Me2C3HN2)3]I}2{1,2-(NH)2C6H4}]

Alobaidi¹,

McWhinnie²,

Hamor³

et al. 1992

J. Chem. Soc., Dalton Trans.

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Section: 750( 1) N( 1 )-O( 1) 1142( 8)supporting

confidence: 91%

Synthesis and electrochemistry of [{Mo(NO)[HB(3,5-Me2C3HN2)3]Cl}2{1,2-(NH)2C6H4}] and the crystal structure of [{Mo(NO)[HB(3,5-Me2C3HN2)3]I}2{1,2-(NH)2C6H4}]

Alobaidi¹,

McWhinnie²,

Hamor³

et al. 1992

J. Chem. Soc., Dalton Trans.

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“…In earlier studies of the reaction between pyridine and the diiodo complex [MoTp*(NO)I 2 ] only the bis-substituted product [MoTp*(NO)(py) 2 ] + could be isolated, 22 although the monosubstituted derivatives [MoTp*(NO)I(NHC n H 2n )] (n ) 4, 5) were isolated with saturated cyclic amines. 23 More recently we have shown 24 IR Spectra. The IR spectra of the new complexes are very similar, and all contain absorptions attributable to the Tp* ligand, including ν max (BH) at ca.…”

Section: Bipyridyl Polyene Complexesmentioning

confidence: 91%

“…The Mo-N(nitrosyl) bond length of 1.896(23) Å is rather long. Previous measurements of this bond in Mo(NO)Tp* complexes have generally resulted in significantly shorter lengths, 1.774(6), 23 1.778(5), 23 1.804(10), 53a 1.751(3), 53b 1.748-(21), 53c and 1.765(5) 29 Å. The N-O bond length at 1.091(34) Å is close to the range of values, 1.1-1.2 Å, in the literature.…”

mentioning

confidence: 91%

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Mono- and Bimetallic Bipyridyl Polyene Complexes Containing 17-Electron Molybdenum Mononitrosyl Centers: Electrochemical, Spectroscopic, and Magnetic Studies

et al. 1996

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The monometallic bipyridyl complexes [MoTp*(NO)X(L-L)] [Tp* = HB(3,5-Me2C3HN2)3; L-L = 3,3‘-bipyridine, 4,4‘-bipyridine, 1,2-bis(4-pyridyl)ethane and X = Cl; L-L = 4,4‘-NC5H4(CHCH) n H4C5N, n = 0, 1, 2, 3, 4 (all trans) and X = Cl, I] and their bimetallic counterparts [{(NO)MoTp*X}2(L-L)] have been synthesized, together with [MoTp*(NO)Cl{4-NC5H4CHCHC(Me)CHCH}]2. The single crystal X-ray structure of [{MoTp*(NO)Cl}2{4,4‘-NC5H4(CHCH)4H4C5N}] confirms that the polyene chain is in the all-trans configuration and exhibits normal bond length alternation with [r C  C−rC  C] = 0.092 Å. The Mo−Mo distance is 20.764(3) Å, and the Mo−N(pyridyl) bond distance of 2.196(6) Å indicates a much lower degree of Mo−(N)ligand π bonding than that found in related amide complexes where Mo−N(amide) distances are typically some 0.3 Å shorter. Cyclic voltammograms of the monometallic complexes contain a single one-electron reduction process, whereas those of the bimetallic complexes contain two one-electron processes. The separation between the two reduction potentials varies almost linearly with polyene chain length from the statistical limit of 36 mV in the bipyridyl dimethyldecapentene derivative to 765 mV in the 4,4‘-bipyridyl derivative. The isovalent bimetallic complexes exhibit EPR signals (300 K) which show hyperfine coupling to two equivalent metal centers with J ≫ A and are consistent with the unpaired electrons occupying orbitals which are predominantly metal in character. Magnetic measurements indicate the presence of an antiferromagnetic interaction in [{MoTp*(NO)Cl}2{4,4‘-NC5H4(CHCH)4H4C5N}] with a coupling −2J estimated to be ca. 80 cm-1 over a distance of ca. 2 nm.

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“…Regarding this last possibility it is notable that the precursor molecules contain 16-electron molybdenum centres in which an sp2 donor atom (0 or N) allows mesomeric contact between the molybdenum centre and the aryl ring of the tetraphenylporphyrin moiety.Z7-'(J In the charge-separated species it would be expected that a 17-electron molybdenum centre bound to an sp3 donor atom would be present, leading to rather different geometric arrangement . 30 Further studies are required to determine the extent of any geometric changes following charge separation in these systems.…”

mentioning

confidence: 99%

Intramolecular electron transfer in peripherally metallated tetraphenyl porphyrin derivatives containing molybdenum mononitrosyl redox centres

Rowley¹,

Kurek²,

George³

et al. 1992

J. Chem. Soc., Chem. Commun.

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Picosecond laser spectroscopy measurements on the novel complexes [Mo(NO)(L)CI(Etpp)] [Etpp = 54E-substituted p h e n y I -1 0,15,20-t r i p h e n y I PO r p h y r i n ; L = h yd rot r i s (3 , 5-d i m et h y I p y razo I -1 -y I) borate , E = para-0, meta-0, ortho-0 ; para-NH] indicate that the observed fluorescence quenching in these compounds is due to fast (T < 30 ps) intramolecular charge separation t o produce transient species with lifetimes in the range 120-290 ps.

show abstract

The formation of amine and amide complexes in the reactions between [Mo(NO){HB(3,5-Me2C3N2H)3}X2] (X = Cl or I) and saturated cyclic amines. The molecular structures of [Mo(NO){HB(3,5-Me2C3N2H)3}I(NHC5H10)] and [Mo(NO){HB(3,5-Me2C3N2H)3}I(NC4H8)]

Cited by 17 publications

References 11 publications

Synthesis and electrochemistry of [{Mo(NO)[HB(3,5-Me2C3HN2)3]Cl}2{1,2-(NH)2C6H4}] and the crystal structure of [{Mo(NO)[HB(3,5-Me2C3HN2)3]I}2{1,2-(NH)2C6H4}]

Synthesis and electrochemistry of [{Mo(NO)[HB(3,5-Me2C3HN2)3]Cl}2{1,2-(NH)2C6H4}] and the crystal structure of [{Mo(NO)[HB(3,5-Me2C3HN2)3]I}2{1,2-(NH)2C6H4}]

Mono- and Bimetallic Bipyridyl Polyene Complexes Containing 17-Electron Molybdenum Mononitrosyl Centers: Electrochemical, Spectroscopic, and Magnetic Studies

Intramolecular electron transfer in peripherally metallated tetraphenyl porphyrin derivatives containing molybdenum mononitrosyl redox centres

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