Preparation and chemistry of novel platinum(II) amide complexes containing .beta.-hydrogens

Bryndza, Henry E.; Fultz, William C.; Tam, William

doi:10.1021/om00124a025

Cited by 55 publications

(29 citation statements)

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“…The Ni−N bond is also inert toward PhSiH 3 . In contrast, the Ni−N bond in the analogous complexes Cp*Ni(PEt 3 )(NHAr) reacts with ROH and R 3 Si−H, whereas the Pt−N bond in L 2 Pt(Me)NR 2 reacts with acetone and acetonitrile 13a…”

Section: Resultsmentioning

confidence: 97%

“…8.3). Metathetic reactions between Ni−halide and −amide salts are also known to lead to Ni−amide species, , but reduction of the starting halides to paramagnetic Ni(I) species is a possible side reaction . The compound (Ind)Ni(PPh 3 )Cl ( 1 ) reacted with LiNHAr (Ar = Ph, 1,3,5-Me 3 C 6 H 2 ), LiNR 2 (R = i -Pr, SiMe 3 , Ph), and sodium imidazole in THF or Et 2 O to give deep green-blue solutions whose 1 H NMR spectra showed the presence of varying quantities of the corresponding HNR 2 species, 1,1‘-biindene (Ind-Ind), OPPh 3 , and (Ind) 2 Ni and broad signals characteristic of the known Ni(I) compound (PPh 3 ) 3 NiCl .…”

Section: Resultsmentioning

confidence: 99%

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Indenylnickel Imidato Complexes: Synthesis, Characterization, and Reactivities

et al. 1998

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The complex (1-Me-indenyl)Ni(PPh3)(phthalimidate) has been prepared and fully characterized by IR and 1H, 13C{1H}, and 31P{1H} NMR spectroscopy and single-crystal X-ray diffraction. The analogous 4,5-dichlorophthalimidato, maleimidato, and succinimidato complexes have also been prepared and characterized spectroscopically. These complexes are thermally stable, in contrast to the analogous Ni−amido species, which could not be prepared. Reactivity studies have shown that the Ni−imidato bond is fairly unreactive in insertion and nucleophilic reactions, and VT 1H NMR studies suggest that the rotation around the Ni−N bond in the maleimidato complex is hindered by ca. 11 kcal/mol. The solid-state structure of the phthalimidato derivative showed that the P, N, C1, and C3 atoms are arranged around the Ni atom in a distorted-square-planar coordination environment, while the C2 atom is within bonding distance above the main square plane. The phthalimidato ligand is η1(N)-coordinated to Ni; the Ni−N bond is relatively short (1.895(4) Å), and the orientation of the imidato ligand is such that the planes bearing the atoms P, Ni, N and C9, N, C16 are rotated by ca. 76° with respect to each other. The hapticity of the indenyl ligand is characterized by an allyl-ene distortion (η5↔η3) and a partial localization of bonding inside the indenyl ring (η3↔η1,η2). 1H and 13C{1H} NMR spectra indicate that the nonsymmetrical coordination of the indenyl ligand, which can be attributed to the different trans influences of the phthalimidato and PPh3 ligands, is maintained in the solution. The character of the Ni−imidato bond has been discussed in terms of electrostatic-covalent and π-bonding interactions.

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

Indenylnickel Imidato Complexes: Synthesis, Characterization, and Reactivities

et al. 1998

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“…According to a search of the Cambridge Structural Database, these are the shortest Pt–N distances reported thus far. For comparison, the Pt(II) amides, cis -Pt(Cl)(NPh 2 )(PEt 3 ) 2 and trans -Pt(H)(NHPh)(PEt 3 ) 2 , feature much longer Pt–N bond lengths of 2.09(2) Å and 2.125(5) Å, respectively, − while the Pt(II) ketimide, [Pt(bpy)Me(NCMe{C(C(Me)O)(C(Me)OH})], features a Pt–N bond length of 2.01(2) Å . The NC bond lengths of the ketimide ligands in 1 (1.256(6), 1.258(2) Å) are typical of carbon–nitrogen distances in other ketimide complexes, − , and the Pt–N–C bond angles in 1 (179.7(4), 178.4(4)°) are consistent with sp hybridization of the N atom. − , Finally, we note that the two ketimide ligands in 1 are coplanar, suggesting that the nitrogen lone pairs on the two [ t Bu 2 CN] − ligands interact with the same Pt(5d) orbital (see further discussion below).…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of a Linear, Two-Coordinate Pt(II) Ketimide Complex

et al. 2019

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Herein we report the synthesis and characterization of a linear, two-coordinate Pt(II) ketimide complex, Pt(N=C t Bu2)2 (1), formed via reaction of PtCl2(1,5-COD) with 2 equiv of Li(N=C t Bu2). Also generated in the reaction is the bimetallic complex, [(t Bu2C=N)Pt(µ-N,C-N=C(t Bu)C(Me)2CH2)Pt(N=C t Bu2)] (2). Both complexes 1 and 2 have been characterized by NMR spectroscopy and X-ray crystallography. Notably, complex 1 exhibits short Pt-N distances (av. Pt-N = 1.817 Å) and an unusually deshielded 195 Pt chemical shift (δPt =-629 ppm) with a large 1 J(195 Pt, 14 N) coupling constant (537 Hz). These data, in combination with a detailed DFT electronic structure analysis, reveal the presence of highly covalent Pt=N multiple bonds formed by a combination of σ-donation, π-donation, and π-backdonation.

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“…Catalytic chemistry of soluble transition-metal complexes with alkylamine substrates is not well developed − even fewer possess β-hydrogens, ,− and few examples have been formed directly from an amine. ,− We communicate the general and reversible activation of primary alkylamine N−H bonds by palladium complexes. These reactions allow for (1) isolation of palladium alkylamides that possess β-hydrogens, (2) the first X-ray structure of a low-valent late-metal alkylamide (3) information on the thermodynamic relationship between a bridging transition-metal hydroxide and its bridging amido analog, (4) strong evidence for an N−H activation mechanism that involves two amines along the pathway toward cleavage of a single amine N−H bond, and (5) an autocatalytic pathway requiring product amine in the reverse extrusion of amine by water.…”

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confidence: 99%