Influence on reactivity of chloro ligand substitution in mononuclear cationic Pd(II) and Pt(II) triphos complexes: X-ray structure of the nitrate derivatives

Fernández, Damián; Sevillano, Paloma; García-Seijo, M. Inés; Castiñeiras, Alfonso; Jánosi, László; Berente, Zoltán; Kollár, László; García-Fernández, M. Esther

doi:10.1016/s0020-1693(00)00329-7

Cited by 19 publications

(14 citation statements)

References 22 publications

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“…From solutions of 4a )]Cl (6a′) were afforded the latter indicating (as previously observed for the squareplanar species [PtCl(triphos)]Cl + KI) 5 that the (2a + KI) metathesis reaction begins with the chloro ligand substitution. The X-ray crystal structures of 4a and 6a′ (Tables 1 and 2) are shown in Fig.…”

Section: Paper Dalton Transactionssupporting

confidence: 70%

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Tuneable reactivity with PPh3 and SnX2 of four- and five-coordinate Pd(ii) and Pt(ii) complexes containing polyphosphines

2013

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The reactivity of the unusual d(8) trigonal-bipyramidal systems [MX(PP3)]X (X = Cl: M = Pd(1a), Pt(2a); X = Br: M = Pd(3a), Pt(4a); X = I: M = Pd(5a), Pt(6a); PP3 = tris[2-(diphenylphosphino)ethyl]phosphine) in CHCl3-CH3OH, the square-pyramidal compounds [MCl(NP3)]Cl (M = Pd(7a); Pt(8a); NP3 = tris[2-(diphenylphosphino)ethyl]amine) in CD3OD-DMF and the distorted square-planar mononuclear [MX(PNP)]X (M = Pd: X = Cl(10a); M = Pt: X = I(10b); PNP = bis[2-(diphenylphosphino)ethyl]amine) and the heteronuclear [PdAu2X4(PP3)] [X = I(9a), Cl(14a), Br(15a)] and [MAuX2(PP3)]X [M = Pd: X = Cl(16a); M = Pt: X = Cl(17a), Br(18a)] species in CDCl3 with PPh3 + SnX2 has been explored to establish the factors that influence the nature of the products. With the mononuclear precursors the course of the reaction is strongly dependent on the tripodal or linear arrangement of the polydentate ligand and in the former case on the halogen. Thus, while for chlorides (1a-2a, 7a-8a) and bromides (3a-4a) the reaction led to the trigonal-bipyramidal compounds [M(SnCl3)(AP3)][SnCl3] [A = P: M = Pd(1), Pt(2); A = N: M = Pd(7), Pt(8)], [MBr(PP3)][SnBr3] [M = Pd(4), Pt(6)] containing M-Sn and M-Br bonds, respectively, for iodides (5a-6a) resulted in the unknown neutral square-planar compounds [MI2(PP(PO)2)(SnI2)2] [M = Pd(9) and Pt(10)] bearing two dangling P=O-SnI2 units and P2MI2 environments. However, complexes of the type [PtCl(PP2PO)X]X' [X = SnCl2, X' = [SnCl3](-)(11)] and [M(PP(PO)2)2X4]X'2 [X = SnCl2, X' = [SnCl3](-): M = Pd(12), Pt(13)] showing P=O-SnCl2 arms were obtained by direct reaction of [PtCl(PP2PO)]Cl (11a) and [M(PP(PO)2)2]Cl2 [M = Pd(12a), Pt(13a)] with SnCl2 in CH3OH. Although complex 9 was also prepared by interaction of the heteronuclear iodide 9a with PPh3 + SnI2 in CDCl3, the use of the neutral and ionic heteronuclear chlorides and bromides (14a-18a) as starting materials afforded the distorted square-planar ionic systems [MAuX'(PP3)(PPh3)][SnX3]2 [M = Pd: X = Cl, X' = SnCl3(-)(14); X = Br, X' = SnBr3(-)(15); M = Pt: X = Cl, X' = SnCl3(-)(17); X = Br, X' = SnBr3(-)(18)] containing M-SnX3 and P-Au-PPh3 functionalities. It was found that these reactions where the heteronuclear species are the precursors proceed via the trigonal-bipyramidal halides not only with X = Cl and Br(1a-4a) but also I(5a). When the precursors were 10a and 10b the reaction occurred with formation of [Pd(PNP)(PPh3)][SnCl3]2 (23) and [Pt(PNP)(PPh3)][SnCl2I]2 (24) showing M-PPh3 units and trihalostannato counter anions.

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Section: Paper Dalton Transactionssupporting

confidence: 70%

“…4d,e However, when a monophosphine interacts with the neutral square-planar systems [PtCl(SnCl 3 )(P 2 )] (P 2 = two monophosphines or chelating diphosphine), the cleavage of the Pt-Sn bond occurs with formation of ionic complexes containing [SnCl 3 ] − as a counter anion. 4f In a previous work 5…”

Section: Introductionmentioning

confidence: 88%

Tuneable reactivity with PPh3 and SnX2 of four- and five-coordinate Pd(ii) and Pt(ii) complexes containing polyphosphines

2013

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“…The Pd-N bond length [2.093(5) Å ] is slightly higher than the same distances for [Pd(PNHP)X]X [X ϭ Cl, 2.061(5) Å ; X ϭ Br, 2.070(5) Å ] in consistence with the higher trans effect of iodo over chloro and bromo ligands [15,22]. On the other hand, the smaller trans influence of the nitrogen over the phosphorus produces a Pd-I bond distance [2.5912(8) The coordination sphere for palladium is tetrahedrally distorted from planar arrangement, with the two phosphorus atoms on one side (0.099/0.101 Å ) of the leastsquares plane defined by [P(1), P(2), N(1), I(1)] and with the nitrogen (0.120 Å ) and the iodine (0.079 Å ) atoms on the opposite side.…”

Section: [Pt(pnhp)i]i ϩ 6au(tdg)clmentioning

confidence: 70%

Synthesis, Characterization, and Reactivity of Cationic Palladium(II) and Platinum(II) Iodo Complexes Containing a Linear or a Tripodal Aminophosphine. The X-Ray Crystal Structures of [Pd{HN(CH2CH2PPh2)2}I]I and [Pd3{N(CH2CH2PPh2}3)2I4]I2Dedicated to Professor Joachim Strähle on the Occasion of his 65th Birthday

García-Seijo

Habtemariam

Fernández-Anca

et al. 2002

Z. anorg. allg. Chem.

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The complexes [M(PNHP)I]I (PNHP ϭ bis[2-(diphenylphosphino)ethyl]amine; M ϭ Pd (1), Pt (2)) and [M(NP 3 )I]I (NP 3 ϭ tris[2-(diphenylphosphino)ethyl]amine; M ϭ Pd (3), Pt (4)) were prepared by interaction of the appropriate aminophosphine in CH 2 Cl 2 with aqueous solutions containing [MCl 4 ] 2Ϫ salts and NaI in a ratio 1:4. Complexes 2 and 3 form the polynuclear compounds [Pt 2 (PNHP) 3 ]I 4 (2a) and [Pd 3 (NP 3 ) 2 I 4 ]I 2 (3a) in the presence of coordinating solvents such as the mixture CD 3 OD/D 2 O/ DMSO-d 6 and CH 2 Cl 2 /CH 3 OH, respectively. Complex 1 consists of distorted square-planar cations [Pd(PNHP)I] ϩ and iodide anions able to establish short N-H···I interactions of 2.850 Å . The aminophosphine adopts a boat conformation and is coordinated to palladium in a tridentate chelating fashion. The crystal structure for cations of 3a reveals the presence of two types of distorted square-planar Pd II atoms, PdNP 2 I and trans-PdP 2 I 2 , NP 3 acting as tridentate chelating and bridging ligand, respectively. On the basis of 31 P { 1 H} NMR data it has been shown that each distorted square-planar Pt(II) centre of 2a contains one PNHP acting as tri-

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“…The two additional phosphor oxide groups of the ligands are not coordinated to the metal centre in the solid state. A long distance of d(Pt1-O4) = 3.524 (3) Å, angles of P1-Pt-O4 of 104.36 (5) ° and P2-Pt-O4 of 99.77 (5) ° are indicative of a weak Pt-NO 3interaction which is much weaker than a previously reported Pt II -NO 3distance of 2.116 Å in a related complex (Fernandez et al, 2001). The nitrate anion is packed within a cavity created by the coordinated phosphine ligand atoms above and due to symmetry below the square plane spanned by the four phosphor ligand atoms creating a distorted octahedral coordination environment around the Pt II ion.…”

Section: S1 Commentmentioning

confidence: 51%

“…For related literature on Pt II complexes, see: Brü ggeller et al (1992). For a structure of a related Pt II nitrato complex, see: Fernandez et al (2001).…”

Section: Related Literaturementioning

confidence: 99%

Bis(1-{bis[2-(diphenylphosphinoyl)ethyl]phosphanyl}-2-(diphenylphosphanyl)ethane)dinitratoplatinum(II) methanol tetrasolvate

2008

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In the title compound, [Pt(NO3)2(C42H42O2P4)2]·4CH3OH, the Pt atom positioned on a crystallographic centre of inversion. The two symmetry-equivalent nitrate anions are weakly coordinated to the PtII ion, creating, together with four P ligand atoms, a distorted octahedral coordination environment. In addition, several close C—H⋯O contacts between the nitrate O atoms and phenyl H atoms are found. Hydrogen bonds from two methanol solvent molecules to one of the O—P groups complete the crystal structure.

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Influence on reactivity of chloro ligand substitution in mononuclear cationic Pd(II) and Pt(II) triphos complexes: X-ray structure of the nitrate derivatives

Cited by 19 publications

References 22 publications

Tuneable reactivity with PPh3 and SnX2 of four- and five-coordinate Pd(ii) and Pt(ii) complexes containing polyphosphines

Tuneable reactivity with PPh3 and SnX2 of four- and five-coordinate Pd(ii) and Pt(ii) complexes containing polyphosphines

Bis(1-{bis[2-(diphenylphosphinoyl)ethyl]phosphanyl}-2-(diphenylphosphanyl)ethane)dinitratoplatinum(II) methanol tetrasolvate

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