Trans-2,6-bis[(dimethylamino)methyl]phenyl-N,N',C complexes of palladium(II) and platinum(II). Crystal structure of [PtI[MeC6H3(CH2NMe2)2-o,o']]BF4: a cyclohexadienyl carbonium ion with a .sigma.-bonded metal substituent

Koten, Gerard van; Grove, David M.; Louwen, Jaap N.; Noltes, J. G.; Spek, Anthony L.; Ubbels, H. J. C.

doi:10.1021/ja00388a022

Cited by 180 publications

(153 citation statements)

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“…The reactions do not require excess transmetalating reagent and can be carried out in an exact 1:1 molar ratio. 8 have been synthesized via organolithium or Grignard reagents. However in a number of cases, alternative methods such as the use of other organometallic reagents or oxidative addition of C-X bonds (which requires the preparation of the corresponding aryl halides) to zerovalent metals are required in order to avoid reduction to metallic Ni or Pd or to prevent the formation of mixtures.…”

Section: Resultsmentioning

confidence: 99%

A Bis(ortho-amine)aryl−Gold(I) Compound as an Efficient, Nontoxic, Arylating Reagent

et al. 2002

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A novel strategy for the synthesis of bis(ortho-amine)chelated monoanionic bisaminoaryl−metal complexes is presented. This method constitutes the exchange of a monoanionic, NCN-pincer ligand (NCN = [C6H3(CH2NMe2)2-2,6]-) between a stable arylgold(I) phosphine, [Au(η1-C-NCN)(PPh3)] (2), and a transition metal halide. This transmetalation results in the quantitative formation of [M(NCN)] organometallic compounds (M = AuIII, NiII, PdII, PtII, TiIV, and FeIII) and [AuCl(PPh3)] as the only coproduct that can be recovered.

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Section: Resultsmentioning

confidence: 99%

A Bis(ortho-amine)aryl−Gold(I) Compound as an Efficient, Nontoxic, Arylating Reagent

et al. 2002

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“…In general, a two-step metallation-trans metallation synthesis procedure can be used in the preparation of transition metal pincer complexes [9,10]. Lithiation of C 6 H 4 (CH 2 NMe 2 ) 2 -1,3 with n BuLi or t BuLi gives the corresponding metallated aryl Li(C 6 H 3 (CH 2 -NMe 2 ) 2 -2,6) which further reacts with [PtCl 2 (SEt 2 ) 2 ] to produce the respective transition metal complex [10].…”

Section: Synthesis and Spectroscopymentioning

confidence: 99%

“…Lithiation of C 6 H 4 (CH 2 NMe 2 ) 2 -1,3 with n BuLi or t BuLi gives the corresponding metallated aryl Li(C 6 H 3 (CH 2 -NMe 2 ) 2 -2,6) which further reacts with [PtCl 2 (SEt 2 ) 2 ] to produce the respective transition metal complex [10]. However, this procedure is not applicable for the synthesis of nitrile-functionalized NCN-pincer complexes since by the reaction of 2a with t BuLi the t Bu anion undergoes nucleophilic attack at the nitrile carbon atom [11].…”

Section: Synthesis and Spectroscopymentioning

confidence: 99%

Synthesis and reaction chemistry of 4-nitrile-substituted NCN-pincer palladium(II) and platinum(II) complexes (NCN=[NC-4-C6H2(CH2NMe2)2-2,6]−)

Köcher

Walfort

Mills

et al. 2008

Journal of Organometallic Chemistry

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a b s t r a c tNitrile-functionalized NCN-pincer complexes of type [MBr(N"C-4-C 6 H 2 (CH 2 NMe 2 ) 2 -2,6)] (6a, M = Pd; 6b, M = Pt) (NCN = [C 6 H 2 (CH 2 NMe 2 ) 2 -2,6] À ) are accessible by the reaction of Br-1-N"C-4-C 6 H 2 -(CH 2 NMe 2 ) 2 -2,6 (2b) with [Pd 2 (dba) 3 Á CHCl 3 ] (5a) (dba = dibenzylidene acetone) and [Pt(tol-4) 2 (SEt 2 )] 2 (5b) (tol = tolyl), respectively. Complex 6b could successfully be converted to the linear coordination polymer {[Pt(N"C-4-C 6 H 2 (CH 2 NMe 2 ) 2 -2,6)](ClO 4 )} n (8) upon its reaction with the organometallic heterobimetallic p-tweezer compound {[Ti](l-r,p-C"CSiMe 3 ) 2 }AgOClO 3 (7) ([Ti] = (g 5 -C 5 H 4 SiMe 3 ) 2 Ti). The structures of 6a (M = Pd) and 6b (M = Pt) in the solid state are reported. In both complexes the d 8 -configurated transition metal ions palladium(II) and platinum(II) possess a somewhat distorted square-planar coordination sphere. Coordination number 4 at the group-10 metal atoms M is reached by the coordination of two ortho-substituents Me 2 NCH 2 , the NCN ipso-carbon atom and the bromide ligand. The N"C group is para-positioned with respect to M.

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“…These complexes were prepared from [MCl(NCN)] (M ) Pt (13), Pd (14), respectively) via halide abstraction with silver nitrate (Scheme 3), according to the procedure reported for the synthesis of [M(NCN)(OH 2 )](BF 4 ) (M ) Pt (11c), Pd (12c); Chart 2). 25 Figure 1. Displacement ellipsoid plot (50% probability level) of the molecular structure of 3a in the crystal, with the adopted labeling scheme.…”

Section: Synthesis and Characterization Of [M(ncn)(no 3 )] Complexesmentioning

confidence: 99%

“…10 The Pt-N(pyridyl) distances (2.141(6) Å for both Pt1-N22 and Pt3-N32) agree with those observed for trans-pyridyl-coordinated N∧C∧N ligands ([Pt(pip 2 NCN)(py)] + (2.138-2.159 Å) 21b,d The puckered five-membered chelate ring conformations, bond lengths, and bond angles of the Pt-NCN moieties fall in the range normally observed for square-planar platinum(II) complexes containing this type of ligand. 25,31 Although both complexes 3a and 16 have distorted squareplanar geometries with torsion angles between 29.8(4)°and 36.2(7)° (Figure 4) for the aryl rings around the platinum center, this should not hamper the possible formation of closed and flat molecular structures such as molecular squares. These complexes have proven to be very flexible in solution because twisting of the arene rings with respect to each other was even observed at low temperatures (vide infra).…”

Section: Synthesis and Characterization Of [M(ncn)(no 3 )] Complexesmentioning

confidence: 99%

Neutral Pyridyl-Functionalized C,N-ortho-Chelated Aminoaryl Platinum(II) Corner Building Blocks for Application in Coordination Reactions

et al. 2005

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Two homoleptic pyridyl-functionalized C,N-ortho-chelating aminoaryl platinum(II) complexes, cis-[Pt(η 2 -C,N)] (3a,b), were prepared via an unconventional method involving the initial synthesis of a bromide-functionalized C,N-chelating aminoaryl platinum(II) precursor complex 8, to which subsequently pyridyl groups were attached via a Suzuki− Miyaura C−C coupling reaction. The electron-donating properties of the pyridyl nitrogen atoms of the resulting complexes (3a,b) were used in complexation reactions with monocationic NCN-pincer (NCN ) [C 6 H 3 (CH 2 NMe 2 ) 2 -2,6] -) platinum(II) (11a) and palladium(II) (12a) nitrate complexes [M(NCN)(NO 3 )], thereby obtaining four trimetallic coordination complexes 16−19. The difference in the pyridine−metal coordination behavior between platinum and palladium was studied by varying the ratios of the reagents and by variable-temperature NMR experiments. IR and Raman analyses of 11a and 12a were performed to determine the coordination behavior of the nitrate counteranion, and it was found that both NO 3 -and H 2 O coordinate to the metal centers. The crystal structure determinations of free pyridyl complex 3a, [Pt(NCN)(NO 3 )] (11a), and [Pt(NCN)(NO 3 )]‚(H 2 O) (11b), as well as the crystal structure of trisplatinum coordination complex 16, are reported.

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Trans-2,6-bis[(dimethylamino)methyl]phenyl-N,N',C complexes of palladium(II) and platinum(II). Crystal structure of [PtI[MeC6H3(CH2NMe2)2-o,o']]BF4: a cyclohexadienyl carbonium ion with a .sigma.-bonded metal substituent

Cited by 180 publications

References 5 publications

A Bis(ortho-amine)aryl−Gold(I) Compound as an Efficient, Nontoxic, Arylating Reagent

A Bis(ortho-amine)aryl−Gold(I) Compound as an Efficient, Nontoxic, Arylating Reagent

Synthesis and reaction chemistry of 4-nitrile-substituted NCN-pincer palladium(II) and platinum(II) complexes (NCN=[NC-4-C6H2(CH2NMe2)2-2,6]−)

Neutral Pyridyl-Functionalized C,N-ortho-Chelated Aminoaryl Platinum(II) Corner Building Blocks for Application in Coordination Reactions

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