Synthesis and characterization of palladium(ii) complexes with new diphosphonium-diphosphine and diphosphine ligands. Production of low molecular weight alternating polyketones via catalytic CO/ethene copolymerisation

Claudio Bianchini; Peter Brüggeller; Carmen Claver; Georg Czermak; Alexander Dumfort; Andrea Meli; Werner Oberhauser; Eduardo J.Garcia Suarez

doi:10.1039/b601154c

Synthesis and characterization of palladium(ii) complexes with new diphosphonium-diphosphine and diphosphine ligands. Production of low molecular weight alternating polyketones via catalytic CO/ethene copolymerisation

Claudio Bianchini^*
, Peter Brüggeller
, Carmen Claver
, Georg Czermak
, Alexander Dumfort
, Andrea Meli
, Werner Oberhauser
, Eduardo J.Garcia Suarez

^*Corresponding author for this work

National Research Council of Italy
University of Innsbruck
Universidad Rovira i Virgili

Research output: Contribution to journal › Article › peer-review

18 Citations (Scopus)

Abstract

The bis-cationic diphosphonium-diphosphine 6,7-di(di-2-methoxyphenyl) phosphinyl-2,2,4,4-tetra(di-2-methoxyphenyl)-2λ⁴, 4λ⁴-diphosphoniumbicyclo[3.1.1]heptane-bis(PF₆) ((o-MeO-PCP)(PF₆)₂) and the diphosphine rac-2,4-bis((di-2-methoxyphenyl)phosphino)pentane (rac-o-MeO-bdpp) have been synthesized. Both ligands have been employed to coordinate PdCl₂ and Pd(OAc)₂ to give [PdCl₂(o-MeO-PCP)](PF₆) ₂ (1a), PdCl₂(rac-o-MeO-bdpp) (1b), [Pd(OAc) ₂(o-MeO-PCP)](PF₆)₂ (2a) and Pd(OAc) ₂(rac-o-MeO-bdpp) (2b). The ligands and complexes have been fully characterized in solution by multinuclear NMR spectroscopy. In addition, 1a and 1b have been authenticated by single crystal X-ray structure analyses. The Pd^II complexes 1a and 1b have been employed as catalyst precursors for the CO/ethene copolymerisation in water-acetic acid mixtures, while 2a and 2b have been tested in methanol in the presence of p-toluenesulfonic acid. Irrespective of the reaction media, perfectly alternating polyketones were obtained in excellent yields and with number-average molecular weights ranging from 7.1-13.9 kg mol^-1 with the diphosphonium-diphosphine catalysts and from 37.2-48.2 kg mol^-1 with the diphosphine catalysts.

Original language	English
Pages (from-to)	2964-2973
Number of pages	10
Journal	Dalton Transactions
Issue number	24
DOIs	https://doi.org/10.1039/b601154c
Publication status	Published - 2006
Externally published	Yes

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Bianchini, C., Brüggeller, P., Claver, C., Czermak, G., Dumfort, A., Meli, A., Oberhauser, W., & Suarez, E. J. G. (2006). Synthesis and characterization of palladium(ii) complexes with new diphosphonium-diphosphine and diphosphine ligands. Production of low molecular weight alternating polyketones via catalytic CO/ethene copolymerisation. Dalton Transactions, (24), 2964-2973. https://doi.org/10.1039/b601154c

@article{8fedeccff6734c1097caec2533606d4b,

title = "Synthesis and characterization of palladium(ii) complexes with new diphosphonium-diphosphine and diphosphine ligands. Production of low molecular weight alternating polyketones via catalytic CO/ethene copolymerisation",

abstract = "The bis-cationic diphosphonium-diphosphine 6,7-di(di-2-methoxyphenyl) phosphinyl-2,2,4,4-tetra(di-2-methoxyphenyl)-2λ4, 4λ4-diphosphoniumbicyclo[3.1.1]heptane-bis(PF6) ((o-MeO-PCP)(PF6)2) and the diphosphine rac-2,4-bis((di-2-methoxyphenyl)phosphino)pentane (rac-o-MeO-bdpp) have been synthesized. Both ligands have been employed to coordinate PdCl2 and Pd(OAc)2 to give [PdCl2(o-MeO-PCP)](PF6) 2 (1a), PdCl2(rac-o-MeO-bdpp) (1b), [Pd(OAc) 2(o-MeO-PCP)](PF6)2 (2a) and Pd(OAc) 2(rac-o-MeO-bdpp) (2b). The ligands and complexes have been fully characterized in solution by multinuclear NMR spectroscopy. In addition, 1a and 1b have been authenticated by single crystal X-ray structure analyses. The PdII complexes 1a and 1b have been employed as catalyst precursors for the CO/ethene copolymerisation in water-acetic acid mixtures, while 2a and 2b have been tested in methanol in the presence of p-toluenesulfonic acid. Irrespective of the reaction media, perfectly alternating polyketones were obtained in excellent yields and with number-average molecular weights ranging from 7.1-13.9 kg mol-1 with the diphosphonium-diphosphine catalysts and from 37.2-48.2 kg mol-1 with the diphosphine catalysts.",

author = "Claudio Bianchini and Peter Br{\"u}ggeller and Carmen Claver and Georg Czermak and Alexander Dumfort and Andrea Meli and Werner Oberhauser and Suarez, \{Eduardo J.Garcia\}",

year = "2006",

doi = "10.1039/b601154c",

language = "English",

pages = "2964--2973",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "24",

}

Bianchini, C, Brüggeller, P, Claver, C, Czermak, G, Dumfort, A, Meli, A, Oberhauser, W & Suarez, EJG 2006, 'Synthesis and characterization of palladium(ii) complexes with new diphosphonium-diphosphine and diphosphine ligands. Production of low molecular weight alternating polyketones via catalytic CO/ethene copolymerisation', Dalton Transactions, no. 24, pp. 2964-2973. https://doi.org/10.1039/b601154c

Synthesis and characterization of palladium(ii) complexes with new diphosphonium-diphosphine and diphosphine ligands. Production of low molecular weight alternating polyketones via catalytic CO/ethene copolymerisation. / Bianchini, Claudio; Brüggeller, Peter; Claver, Carmen et al.
In: Dalton Transactions, No. 24, 2006, p. 2964-2973.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Synthesis and characterization of palladium(ii) complexes with new diphosphonium-diphosphine and diphosphine ligands. Production of low molecular weight alternating polyketones via catalytic CO/ethene copolymerisation

AU - Bianchini, Claudio

AU - Brüggeller, Peter

AU - Claver, Carmen

AU - Czermak, Georg

AU - Dumfort, Alexander

AU - Meli, Andrea

AU - Oberhauser, Werner

AU - Suarez, Eduardo J.Garcia

PY - 2006

Y1 - 2006

N2 - The bis-cationic diphosphonium-diphosphine 6,7-di(di-2-methoxyphenyl) phosphinyl-2,2,4,4-tetra(di-2-methoxyphenyl)-2λ4, 4λ4-diphosphoniumbicyclo[3.1.1]heptane-bis(PF6) ((o-MeO-PCP)(PF6)2) and the diphosphine rac-2,4-bis((di-2-methoxyphenyl)phosphino)pentane (rac-o-MeO-bdpp) have been synthesized. Both ligands have been employed to coordinate PdCl2 and Pd(OAc)2 to give [PdCl2(o-MeO-PCP)](PF6) 2 (1a), PdCl2(rac-o-MeO-bdpp) (1b), [Pd(OAc) 2(o-MeO-PCP)](PF6)2 (2a) and Pd(OAc) 2(rac-o-MeO-bdpp) (2b). The ligands and complexes have been fully characterized in solution by multinuclear NMR spectroscopy. In addition, 1a and 1b have been authenticated by single crystal X-ray structure analyses. The PdII complexes 1a and 1b have been employed as catalyst precursors for the CO/ethene copolymerisation in water-acetic acid mixtures, while 2a and 2b have been tested in methanol in the presence of p-toluenesulfonic acid. Irrespective of the reaction media, perfectly alternating polyketones were obtained in excellent yields and with number-average molecular weights ranging from 7.1-13.9 kg mol-1 with the diphosphonium-diphosphine catalysts and from 37.2-48.2 kg mol-1 with the diphosphine catalysts.

AB - The bis-cationic diphosphonium-diphosphine 6,7-di(di-2-methoxyphenyl) phosphinyl-2,2,4,4-tetra(di-2-methoxyphenyl)-2λ4, 4λ4-diphosphoniumbicyclo[3.1.1]heptane-bis(PF6) ((o-MeO-PCP)(PF6)2) and the diphosphine rac-2,4-bis((di-2-methoxyphenyl)phosphino)pentane (rac-o-MeO-bdpp) have been synthesized. Both ligands have been employed to coordinate PdCl2 and Pd(OAc)2 to give [PdCl2(o-MeO-PCP)](PF6) 2 (1a), PdCl2(rac-o-MeO-bdpp) (1b), [Pd(OAc) 2(o-MeO-PCP)](PF6)2 (2a) and Pd(OAc) 2(rac-o-MeO-bdpp) (2b). The ligands and complexes have been fully characterized in solution by multinuclear NMR spectroscopy. In addition, 1a and 1b have been authenticated by single crystal X-ray structure analyses. The PdII complexes 1a and 1b have been employed as catalyst precursors for the CO/ethene copolymerisation in water-acetic acid mixtures, while 2a and 2b have been tested in methanol in the presence of p-toluenesulfonic acid. Irrespective of the reaction media, perfectly alternating polyketones were obtained in excellent yields and with number-average molecular weights ranging from 7.1-13.9 kg mol-1 with the diphosphonium-diphosphine catalysts and from 37.2-48.2 kg mol-1 with the diphosphine catalysts.

UR - https://www.scopus.com/pages/publications/33745021833

U2 - 10.1039/b601154c

DO - 10.1039/b601154c

M3 - Article

AN - SCOPUS:33745021833

SN - 1477-9226

SP - 2964

EP - 2973

JO - Dalton Transactions

JF - Dalton Transactions

IS - 24

ER -

Synthesis and characterization of palladium(ii) complexes with new diphosphonium-diphosphine and diphosphine ligands. Production of low molecular weight alternating polyketones via catalytic CO/ethene copolymerisation

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