Stereochemistry of 5-Coordinated Compounds. II. On the Configuration of the Nickel Compound [NiBr3(Et3P)2].

Jensen, Kai Arne; Nygaard, Børge; Laaksonen, Terttu; Hakala, Maire

doi:10.3891/acta.chem.scand.03-0474

Cited by 35 publications

(9 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…33 Similar compounds have been prepared also by oxidative addition or via nucleophilic displacement of bromo ligands starting from a Ni(II) precursor. 17,18, 34 The formation of complex 3 can be explained by a radical reaction mechanism previously outlined by Fahey et al 35 Such a mechanism is consistent with the observed formation of 1-bromo-2,2difluoroethene, which could be detected by 19 F and 1 H NMR spectroscopy. 36 Compound 1 can be converted into cationic complexes of the general composition trans-[Ni(CF᎐ ᎐ CF 2 )(L)(PEt 3 ) 2 ]BArЈ 4 (4: L = NCMe; 5: L = CO; 6: CN t Bu).…”

Section: Discussionsupporting

confidence: 61%

“…If the reaction is carried out in hexane instead of toluene as a solvent no oxidative addition product is formed and the compound [NiBr 2 (PEt 3 ) 2 ] (3) is isolated instead. 19 The presence of the difluorovinyl group in 2 is revealed by two doublet of triplets in the 19 F NMR spectrum at δ Ϫ91.63 (J FF = 74.5, J PF = 6.8 Hz) and δ Ϫ67.47 (J FF = 75.7, J PF = 6.9 Hz). An absorption band at 1692 cm Ϫ1 in the IR spectrum is characteristic for a fluorovinyl ligand at nickel.…”

Section: Formation Of Trans-[nibr(cbr᎐mentioning

confidence: 99%

See 1 more Smart Citation

Synthesis, structure and reactivity of fluorovinyl nickel complexes: formation of a phosphonioethenyl complexDedicated to Professor Dieter Naumann on the occasion of his 60th birthday.

Braun

Blöcker

Schorlemer

et al. 2002

J. Chem. Soc., Dalton Trans.

View full text Add to dashboard Cite

Section: Discussionsupporting

confidence: 61%

Section: Formation Of Trans-[nibr(cbr᎐mentioning

confidence: 99%

Synthesis, structure and reactivity of fluorovinyl nickel complexes: formation of a phosphonioethenyl complexDedicated to Professor Dieter Naumann on the occasion of his 60th birthday.

Braun

Blöcker

Schorlemer

et al. 2002

J. Chem. Soc., Dalton Trans.

View full text Add to dashboard Cite

“…symmetry is shown in Figure 2. In this, the numbers in A schematic diagram of a complex with (12) H Yamatera, Bull. Chem.…”

Section: Angular Overlap Modelmentioning

confidence: 99%

Single-crystal electronic spectrum of bromotetrakis(2-methylimidazole)nickel(II) bromide and an interpretation of the energy levels of some tetragonally distorted nickel complexes using the angular overlap model

Hitchman¹

1972

Inorg. Chem.

View full text Add to dashboard Cite

the range of thermodynamic discrimination, covers four orders of magnitude. This is in contrast with the reactivity patterns for the reactions of HONO where the rate constants for the formation of XNO are practically independent of the nature of X-. In the case of HNOz i t was concluded that no N-X bond making obtains in the transition state. Therefore, in the case of C O ( N H~)~O N O~+ , there must be some N-X bond making in the transition state. A "quantitative" measure of the amount of bond breaking and bond making that obtains in the transition state can be estimated from the log k vs. log Q plot presented in Figure 1. Assuming a linear free energy relationship, we obtain a slope of -0.5, a value which suggests approximately "equal" contributions of bond making and bond breaking in the transition state for the reaction.Finally, i t is noteworthy that the catalysis of aquation of Co(NH3)50N02+ by halides and thiocyanate ions, when combined with microscopic reversibility considerations, indicates that, provided the equilibrium is favorable, 0-nitrosation on co(NH3)60H2+ would be accomplished by XNO. Thus, the range of reagents involved in nitrosation in inorganic chemistry has been extended from the early studies with Nd&336 to the more recent studies implicating NO+ 6 -Q and to the present studies which show the importance of reaction paths involving nitrosyl halides and nitrosyl thiocyanate. We are planning to extend the studies of the effects of halides and pseudohalides to other metal complexes containing coordinated nitrite and coordinated nitrosyl.The single-crystal polarized electronic spectrum of the five-coordinate complex bromotetrakis(2-methylimidazole)nickel(II ) bromide is reported. A general method for the analysis of the excited-state energies observed in the "d-d" electronic spectra of nickel halide complexes with D4h or C4, , symmetry is described and used to derive the angular overlap u-and *-bonding parameters of the ligands in several nickel halide complexes of known crystal structure. IntroductionThere has been considerable interest recently both in the electronic spectra of five-coordinate nickel complexesl and in the interpretatioa of the energy levels of tetragonally distorted compounds using ligand-field bonding parameters.2 The single-crystal spectrum of bromotetrakis(2-methylimidazole)nickel(II) bromide, [Ni(2-meim)qBr]Br, is therefore interesting both because i t is a representative example of the spectrum of a square-pyramidal nickel complex and because it allows the ligand u-and .rr-bonding parameters of a fivecoordinate complex to be compared with those of similar six-coordinate compounds.

show abstract

“…This was shown to be monomeric in Br Ni Br \ / ---P(C2Hg)3 V freezing benzene; this is most readily explained by assuming that the nickel atom is five-covalent. Later (98) it was shown that the compound is paramagnetic, containing one unpaired electron per nickel atom (µ = 1.7-1.9 Bohr magnetons); this supports the tervalency assigned to the nickel atom. From the electric dipole moment (2.5 D) it was concluded that the bipyramidal structure could be excluded and the square pyramid arrangement shown in formula V was proposed.…”

Section: A Five-covalent Complexesmentioning

confidence: 64%

The Stereochemistry and Valence States of Nickel.

Nyholm¹

1953

Chem. Rev.

View full text Add to dashboard Cite

Stereochemistry of 5-Coordinated Compounds. II. On the Configuration of the Nickel Compound [NiBr3(Et3P)2].

Cited by 35 publications

References 0 publications

Synthesis, structure and reactivity of fluorovinyl nickel complexes: formation of a phosphonioethenyl complexDedicated to Professor Dieter Naumann on the occasion of his 60th birthday.

Synthesis, structure and reactivity of fluorovinyl nickel complexes: formation of a phosphonioethenyl complexDedicated to Professor Dieter Naumann on the occasion of his 60th birthday.

Single-crystal electronic spectrum of bromotetrakis(2-methylimidazole)nickel(II) bromide and an interpretation of the energy levels of some tetragonally distorted nickel complexes using the angular overlap model

The Stereochemistry and Valence States of Nickel.

Contact Info

Product

Resources

About