2011
DOI: 10.1039/c1dt10963d
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Abstract: One bond Pt-P coupling constants (1)J(PtP) of a series of cationic complexes [PtXL(PPh(3))(2)](+) (X = NO(3), Cl, Br, I; L = 4-Z-pyridines, Z = electron withdrawing or releasing groups, 4a-k; or X = Cl, L = NH(3), PhCH(2)NH(2) and (i)PrNH(2), 5a-c) have been used to establish the trans and cis influence sequences of X and pyridines. The crystal structure of compound 4f(BF(4)) with Z = (t)Bu has been resolved. In the pyridine complexes 4a-d (Z = H, variable X), both the trans and cis influence series of the ani… Show more

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Cited by 17 publications
(9 citation statements)
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“…In our consideration, we assume that the s-a nd p-modes are the major resonance structures as shown in Scheme 1, although this does not mean the nonexistence of other minor resonance structures.T he n s values derived from each bond of dicationic tris-nitrile Thec orrelation between the sp continuum and intramolecular charge transfer was examined by the natural atomic orbital (NAO) Scheme 4. [3a, 9] This trend clearly showed that the strong charge transfer between the indole ligand and am etal center leads to an increase of the s-character.T he phosphine ligands are capable of delocalizing cationic charge of acomplex, [16] which weakens the electron-accepting ability of am etal center. [3a, 9] This trend clearly showed that the strong charge transfer between the indole ligand and am etal center leads to an increase of the s-character.T he phosphine ligands are capable of delocalizing cationic charge of acomplex, [16] which weakens the electron-accepting ability of am etal center.…”
Section: Methodsmentioning
confidence: 99%
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“…In our consideration, we assume that the s-a nd p-modes are the major resonance structures as shown in Scheme 1, although this does not mean the nonexistence of other minor resonance structures.T he n s values derived from each bond of dicationic tris-nitrile Thec orrelation between the sp continuum and intramolecular charge transfer was examined by the natural atomic orbital (NAO) Scheme 4. [3a, 9] This trend clearly showed that the strong charge transfer between the indole ligand and am etal center leads to an increase of the s-character.T he phosphine ligands are capable of delocalizing cationic charge of acomplex, [16] which weakens the electron-accepting ability of am etal center. [3a, 9] This trend clearly showed that the strong charge transfer between the indole ligand and am etal center leads to an increase of the s-character.T he phosphine ligands are capable of delocalizing cationic charge of acomplex, [16] which weakens the electron-accepting ability of am etal center.…”
Section: Methodsmentioning
confidence: 99%
“…Communications 5324 www.angewandte.org population analysis.P ositive charge on the N-methylindole moiety in h 1 -indole complexes decreased in the following order: N-methylindolium (+ 1) > 3-Me' ' (+ 0.80) > 4-Me' ' (+ 0.37) > GaCl 3 (Nmethylindole) (+ 0.23), AlCl 3 (N-methylindole) (+ 0.19) > N-methylindole (0). This trend clearly showed that the strong charge transfer between the indole ligand and am etal center leads to an increase of the s-character.T he phosphine ligands are capable of delocalizing cationic charge of acomplex, [16] which weakens the electron-accepting ability of am etal center. [17] Thus,t he auxiliary ligands largely affect the s-p state of indole complexes.Itshould be noted that the positive charge of the indole ligand in the p(h 2 )complex 5-Me' ' (+ 0.25) or 6-Me (+ 0.28) is in the range of those found for h 1 -s/pintermediate-complexes.T his may suggest that as ubtle change of the charge transfer ability,a sw ell as of any other factors,c auses as hift between the s/p-intermediate-and pmodes in the region of weak charge transfer.…”
Section: Angewandte Chemiementioning
confidence: 99%
“…This can be understood in terms of the cis influence of the methyl ligand. According to recent studies [80], the cis influence is related to the ability of a ligand to lower the charge of the metal centre and can have the same "direction" as the trans influence [80][81][82][83] or the opposite [80,84,85]. The methyl group in the [(COD)Pt(Me)] complexes obviously exhibits a cis influence in the opposite direction to the trans influence (negative cis influence).…”
Section: Nmr Spectroscopy -The Strength Of the Pt-s Bondmentioning
confidence: 97%
“…This is on first view contradictory to the massive lowering of the positive charge of the Pt atom through the strong σ-donor behaviour of the methyl ligand. However, detailed calculations on the system cis-[Pt(PPh 3 ) 2 Cl(4-Z-pyridine)] + showed that electron withdrawing Z groups on the pyridine ligand reduce the negative charge on the N atom and the positive charge on the Pt atom at the same time [80]. Or in other words, they decrease the electronegativity difference and increase the covalency of the N-Pt bond.…”
Section: Nmr Spectroscopy -The Strength Of the Pt-s Bondmentioning
confidence: 98%
“…[3a, 9] This trend clearly showed that the strong charge transfer between the indole ligand and am etal center leads to an increase of the s-character.T he phosphine ligands are capable of delocalizing cationic charge of acomplex, [16] which weakens the electron-accepting ability of am etal center. [17] Thus,t he auxiliary ligands largely affect the s-p state of indole complexes.Itshould be noted that the positive charge of the indole ligand in the p( Thus,o ur experimental and theoretical results showed that there is the s-p continuum in indole-Pd II complexes.The s-p continuum has been previously observed in the h 1 -arenemetal complexes, [18,19] although the pure s-complexes of arenes (Wheland-intermediate-type) have been rarely identified due to the insufficient charge transfer between the arene ligand and am etal center.…”
mentioning
confidence: 99%