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

Damián Fernández, Paloma Sevillano, M. Inés García-Seijo, Alfonso Castieiras, László Jánosi, Z. Berente, L. Kollár, M. Esther García-Fernández

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Abstract

The substitution of chloro ligand in [M(triphos)Cl]Cl complexes [M = Pd (1), Pt (2); triphos = Ph2PC2H4P(Ph)C2H4 PPh2] by reaction with 1 equiv. of KX resulted in the formation of the ionic complexes [M(triphos)X]Cl [X = I, M = Pd (3), Pt (4); X = CN, M = Pd (5), Pt (6)]. Methanolic solutions of silver nitrate in excess displace the chloro ligand and counterion of 1 and 2, giving rise to the formation of the crystalline complexes [M(triphos)(ONO2)](NO3) [M = Pd (7), Pt (8)] suitable for X-ray diffraction studies. The complexes show a distorted square-planar environment around the metal, there being three coordination sites occupied by phosphorus atoms from the triphos and the fourth by the oxygen atom from a nitrate acting as monodentate ligand. A second NO3 - is acting as counterion with D3h symmetry. The use of a high excess of SnCl2 in the presence of 1 equiv. of PPh3 enabled the formation of complexes [M(triphos)(PPh3)](SnCl3)2 [M = Pd (9), Pt (10)]. These complexes, in addition to [M(triphos)X]X [X = Br, M = Pd (1a), Pt (2a); X = I, M = Pd (1b), Pt (2b)], were synthesised and all Pt(II) complexes characterised by microanalysis. Mass spectrometry, IR spectroscopy, NMR spectroscopy and conductivity measurements were also used for characterisation. The structure and reactivity studies in solution were carried out by 31P{1H} NMR. The trends in chemical shifts δ (P) and 1J(195Pt,31P) coupling constants were used to establish a sequence in the X ligand exchange reactions. While [Pd(triphos)I]I (1b) undergoes a ring-opening reaction by titration with AuI, the analogous Pt(II) complex (2b) does not react. The formation of new five-coordinate Pd(II) and Pt(II) complexes was observed by titration of 5-8 with potassium cyanide.

Original languageEnglish
Pages (from-to)40-52
Number of pages13
JournalInorganica Chimica Acta
Volume312
Issue number1-2
DOIs
Publication statusPublished - Jan 29 2001

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Nitrates
nitrates
Substitution reactions
reactivity
Ligands
X-Rays
substitutes
Derivatives
X rays
ligands
Titration
titration
x rays
Potassium Cyanide
Silver Nitrate
Atoms
silver nitrates
nuclear magnetic resonance
Cyanides
Microanalysis

Keywords

  • Crystal structures
  • Cyano complexes
  • M(II)-triphos systems
  • Monodentate ligand substitutions
  • NMR spectroscopy
  • Palladium(II) complexes
  • Platinum(II) complexes

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

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; Castieiras, Alfonso; Jánosi, László; Berente, Z.; Kollár, L.; García-Fernández, M. Esther.

In: Inorganica Chimica Acta, Vol. 312, No. 1-2, 29.01.2001, p. 40-52.

Research output: Contribution to journalArticle

Fernández, Damián ; Sevillano, Paloma ; García-Seijo, M. Inés ; Castieiras, Alfonso ; Jánosi, László ; Berente, Z. ; Kollár, L. ; García-Fernández, M. Esther. / Influence on reactivity of chloro ligand substitution in mononuclear cationic Pd(II) and Pt(II) triphos complexes : X-ray structure of the nitrate derivatives. In: Inorganica Chimica Acta. 2001 ; Vol. 312, No. 1-2. pp. 40-52.
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abstract = "The substitution of chloro ligand in [M(triphos)Cl]Cl complexes [M = Pd (1), Pt (2); triphos = Ph2PC2H4P(Ph)C2H4 PPh2] by reaction with 1 equiv. of KX resulted in the formation of the ionic complexes [M(triphos)X]Cl [X = I, M = Pd (3), Pt (4); X = CN, M = Pd (5), Pt (6)]. Methanolic solutions of silver nitrate in excess displace the chloro ligand and counterion of 1 and 2, giving rise to the formation of the crystalline complexes [M(triphos)(ONO2)](NO3) [M = Pd (7), Pt (8)] suitable for X-ray diffraction studies. The complexes show a distorted square-planar environment around the metal, there being three coordination sites occupied by phosphorus atoms from the triphos and the fourth by the oxygen atom from a nitrate acting as monodentate ligand. A second NO3 - is acting as counterion with D3h symmetry. The use of a high excess of SnCl2 in the presence of 1 equiv. of PPh3 enabled the formation of complexes [M(triphos)(PPh3)](SnCl3)2 [M = Pd (9), Pt (10)]. These complexes, in addition to [M(triphos)X]X [X = Br, M = Pd (1a), Pt (2a); X = I, M = Pd (1b), Pt (2b)], were synthesised and all Pt(II) complexes characterised by microanalysis. Mass spectrometry, IR spectroscopy, NMR spectroscopy and conductivity measurements were also used for characterisation. The structure and reactivity studies in solution were carried out by 31P{1H} NMR. The trends in chemical shifts δ (P) and 1J(195Pt,31P) coupling constants were used to establish a sequence in the X ligand exchange reactions. While [Pd(triphos)I]I (1b) undergoes a ring-opening reaction by titration with AuI, the analogous Pt(II) complex (2b) does not react. The formation of new five-coordinate Pd(II) and Pt(II) complexes was observed by titration of 5-8 with potassium cyanide.",
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T1 - Influence on reactivity of chloro ligand substitution in mononuclear cationic Pd(II) and Pt(II) triphos complexes

T2 - X-ray structure of the nitrate derivatives

AU - Fernández, Damián

AU - Sevillano, Paloma

AU - García-Seijo, M. Inés

AU - Castieiras, Alfonso

AU - Jánosi, László

AU - Berente, Z.

AU - Kollár, L.

AU - García-Fernández, M. Esther

PY - 2001/1/29

Y1 - 2001/1/29

N2 - The substitution of chloro ligand in [M(triphos)Cl]Cl complexes [M = Pd (1), Pt (2); triphos = Ph2PC2H4P(Ph)C2H4 PPh2] by reaction with 1 equiv. of KX resulted in the formation of the ionic complexes [M(triphos)X]Cl [X = I, M = Pd (3), Pt (4); X = CN, M = Pd (5), Pt (6)]. Methanolic solutions of silver nitrate in excess displace the chloro ligand and counterion of 1 and 2, giving rise to the formation of the crystalline complexes [M(triphos)(ONO2)](NO3) [M = Pd (7), Pt (8)] suitable for X-ray diffraction studies. The complexes show a distorted square-planar environment around the metal, there being three coordination sites occupied by phosphorus atoms from the triphos and the fourth by the oxygen atom from a nitrate acting as monodentate ligand. A second NO3 - is acting as counterion with D3h symmetry. The use of a high excess of SnCl2 in the presence of 1 equiv. of PPh3 enabled the formation of complexes [M(triphos)(PPh3)](SnCl3)2 [M = Pd (9), Pt (10)]. These complexes, in addition to [M(triphos)X]X [X = Br, M = Pd (1a), Pt (2a); X = I, M = Pd (1b), Pt (2b)], were synthesised and all Pt(II) complexes characterised by microanalysis. Mass spectrometry, IR spectroscopy, NMR spectroscopy and conductivity measurements were also used for characterisation. The structure and reactivity studies in solution were carried out by 31P{1H} NMR. The trends in chemical shifts δ (P) and 1J(195Pt,31P) coupling constants were used to establish a sequence in the X ligand exchange reactions. While [Pd(triphos)I]I (1b) undergoes a ring-opening reaction by titration with AuI, the analogous Pt(II) complex (2b) does not react. The formation of new five-coordinate Pd(II) and Pt(II) complexes was observed by titration of 5-8 with potassium cyanide.

AB - The substitution of chloro ligand in [M(triphos)Cl]Cl complexes [M = Pd (1), Pt (2); triphos = Ph2PC2H4P(Ph)C2H4 PPh2] by reaction with 1 equiv. of KX resulted in the formation of the ionic complexes [M(triphos)X]Cl [X = I, M = Pd (3), Pt (4); X = CN, M = Pd (5), Pt (6)]. Methanolic solutions of silver nitrate in excess displace the chloro ligand and counterion of 1 and 2, giving rise to the formation of the crystalline complexes [M(triphos)(ONO2)](NO3) [M = Pd (7), Pt (8)] suitable for X-ray diffraction studies. The complexes show a distorted square-planar environment around the metal, there being three coordination sites occupied by phosphorus atoms from the triphos and the fourth by the oxygen atom from a nitrate acting as monodentate ligand. A second NO3 - is acting as counterion with D3h symmetry. The use of a high excess of SnCl2 in the presence of 1 equiv. of PPh3 enabled the formation of complexes [M(triphos)(PPh3)](SnCl3)2 [M = Pd (9), Pt (10)]. These complexes, in addition to [M(triphos)X]X [X = Br, M = Pd (1a), Pt (2a); X = I, M = Pd (1b), Pt (2b)], were synthesised and all Pt(II) complexes characterised by microanalysis. Mass spectrometry, IR spectroscopy, NMR spectroscopy and conductivity measurements were also used for characterisation. The structure and reactivity studies in solution were carried out by 31P{1H} NMR. The trends in chemical shifts δ (P) and 1J(195Pt,31P) coupling constants were used to establish a sequence in the X ligand exchange reactions. While [Pd(triphos)I]I (1b) undergoes a ring-opening reaction by titration with AuI, the analogous Pt(II) complex (2b) does not react. The formation of new five-coordinate Pd(II) and Pt(II) complexes was observed by titration of 5-8 with potassium cyanide.

KW - Crystal structures

KW - Cyano complexes

KW - M(II)-triphos systems

KW - Monodentate ligand substitutions

KW - NMR spectroscopy

KW - Palladium(II) complexes

KW - Platinum(II) complexes

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