Chemical syntheses with metal atoms

Blackborow, J. R.; Eady, Colin R.; Gustorf, E. A. Koerner Von; Scrivanti, Alberto; Wolfbeis, Otto S.

doi:10.1016/s0022-328x(00)92025-4

Cited by 27 publications

(9 citation statements)

References 6 publications

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“…The IR spectrum of this complex showed characteristic bands due to bridging acetato ligand at 1585 and 1420 cm'1.22 In the NMR spectrum at 40 °C, methyl protons of the µ-acetato groups appeared as one sharp singlet at 1.99, indicating that 3 has only an ( -C1, b-N)-(g-N, /¡-C*)-type configuration and contains no (a-C1, ó-N)-(g-C', A-N)-type one (Figure 3). 15 In consideration of the fact that two coordination planes in an acetato-bridged cyclopalladated dimer are combined by two mutually cis µacetato ligands with about 24°of dihedral angle,23 3 was expected to have three conformations, C, D, and E, as shown in Figure 3 low temperature. However, the conformations D and E are less favorable, because molecular models indicate that the phenylene and pyridyl protons in conformation D are located very close to each other and that two methylene groups in conformation E collide with each other.…”

Section: Ch2ch2coch3)+]mentioning

confidence: 99%

Preparation and characterization of novel six-membered cyclopalladated complexes of 2-benzylpyridine

Hiraki¹,

Fuchita²,

Takechi³

1981

Inorg. Chem.

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I. It consists of a unique zigzag chain structure in which the distorted [(C3H7)2NCS2T1]2 dimers are connected by interdimer Tl-S linkages such that one T1(I) is six-coordinate while the other is five-coordinate. Instead of an eight-membered ring, it exists as a distorted bipyramid with T1(I) atoms at the apices.Acknowledgment is made to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for partial support of this research.Registry No. [Au(S2CN(C2H5)2)SCN]2, 79255-13-3; [Au(S2C-N(C2H5)2)2][Au(SCN)2], [Au(S2CN(C2H5)2)SeCN]2, 79255-15-5; [Au(S2CN(C2H5)2)2][Au(SeCN)2], 2)Br]2, 79255-18-8; [Au(S2CN(C2H5)2)2][AuBr2], 33916-73-3; [Au(S2CN(C2H5)2)I]2, 79255-19-9; [Au(S2CN(C2-H5)2)2][AuI2], 79255-20-2; [Au(S2CN(C2H5)2)2][Au(SCN)2Br2], 79255-22-4; [Au(S2CN(C4H,)2)SCN]2, 79255-23-5; [Au(S2CN-(C4H9)2)2][Au(SCN)2], [Ag(S2CN(C2H5)2)]6, 59859-16-4; [Au(S2CN(C2H5)2)]2, 66712-10-5; [Au(S2CN(C4H9)2)]2, 59306-90-0; (SCN)2, 505-14-6; (SeCN)2,27151-67-3; Br2, 7726-95-6; I2, 7553-56-2.

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Section: Ch2ch2coch3)+]mentioning

confidence: 99%

Preparation and characterization of novel six-membered cyclopalladated complexes of 2-benzylpyridine

Hiraki¹,

Fuchita²,

Takechi³

1981

Inorg. Chem.

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“…It is evident that a steric effect is operative in our systems, preventing the coordination of a fourth olefin. However, this effect is not sufficiently dominant to preclude tris(olefin) complex formation even with bulky substituents on the olefin, as seen, for example, by the metal-vapor synthesis of tris(styrene)nickel by Blackborow and co-workers, 24 It is, however, the interpretation of the optical spectral data for these systems and the rationalization of the observed trends with respect to both substituent effect and stoichiometry that are the most intriguing aspects of this study. Before we proceed with a detailed analysis, we must again refer to our reinvestigation of the nickel-ethylene system and, in the light of the new data, modify our explanation of the optical spectra of the analogous Ni/C2F4 complexes.…”

Section: Resultsmentioning

confidence: 99%

Nickel atom-olefin chemistry. Investigation of the optical spectra of binary nickel-olefin complexes

Ozin¹,

Power²

1978

Inorg. Chem.

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Cocondensation of nickel atoms with simple alkyl, fluoro, or chloro olefins, in the temperature range 10-77 K, has resulted in a large series of binary complexes of the type Ni(ol)" (where = 1-3). A characteristic feature of these complexes is an intense absorption in the ultraviolet. This transition is only slightly sensitive to the substituent(s) on the coordinated olefin but highly sensitive to the number of coordinated olefins. Observed trends in the optical spectra are interpreted in terms of electronic transitions mainly localized on the nickel atom, and a correlation is observed between the transition energies of the mono(olefin)nickel complexes and the it* orbital energy of the free olefin. Similar results have been obtained with a variety of palladium-olefin cocondensations. The complexes show a fair degree of thermal stability in the matrices studied. This, coupled with the absence of any evidence of oxidative addition, implies the metal-atom technique may be a general tool for the synthesis of such transition-metal it complexes.

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“…The first reports on the reaction between RE metal vapors and organic substrates ( e.g. , 1-hexyne, 3-hexyne, 1,3-butadiene, 2,4-pentanedione, and cyclooctatetraene) were presented by Blackborow, 223 Evans, 224 , 225 and DeKock. 222 , 226 By reacting RE metal atoms (RE = La, Ce, Nd, Er) with C 8 H 8 ( Scheme 34 ), DeKock and co-workers isolated a family of asymmetric complexes of formula [RE(COT)(THF) 2 ][RE(COT) 2 ] ( 92-RE ; RE = La, Ce, Nd, Er), while reactivity with Yb afforded “Yb(COT)” ( 5 ), previously obtained from reaction in liquid NH 3 ( vide supra , Scheme 4 ).…”

Section: Metals As Synthetic Precursorsmentioning

confidence: 99%

Rare Earth Starting Materials and Methodologies for Synthetic Chemistry

Ortu

2022

Chem. Rev.

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The number of rare earth (RE) starting materials used in synthesis is staggering, ranging from simple binary metal-halide salts to borohydrides and “designer reagents” such as alkyl and organoaluminate complexes. This review collates the most important starting materials used in RE synthetic chemistry, including essential information on their preparations and uses in modern synthetic methodologies. The review is divided by starting material category and supporting ligands ( i.e. , metals as synthetic precursors, halides, borohydrides, nitrogen donors, oxygen donors, triflates, and organometallic reagents), and in each section relevant synthetic methodologies and applications are discussed.

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Chemical syntheses with metal atoms

Cited by 27 publications

References 6 publications

Preparation and characterization of novel six-membered cyclopalladated complexes of 2-benzylpyridine

Preparation and characterization of novel six-membered cyclopalladated complexes of 2-benzylpyridine

Nickel atom-olefin chemistry. Investigation of the optical spectra of binary nickel-olefin complexes

Rare Earth Starting Materials and Methodologies for Synthetic Chemistry

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