Versatile phosphite ligands based on silsesquioxane backbones

J I van der Vlugt; J Ackerstaff; T W Dijkstra; A M Mills; H Kooijman; A L Spek; A Meetsma; H C L Abbenhuis; D Vogt

doi:10.1002/adsc.200303186

Versatile phosphite ligands based on silsesquioxane backbones

J I van der Vlugt, J Ackerstaff, T W Dijkstra, A M Mills, H Kooijman, A L Spek, A Meetsma, H C L Abbenhuis, D Vogt^*

^*Corresponding author for this work

Research output: Contribution to journal › Review article › peer-review

29 Citations (Scopus)

Abstract

Silsesquioxanes are employed as ligand backbones for the synthesis of novel phosphite compounds with 3,3'-5,5'-tetrakis(tert-butyl)-2,2'-di-oxa-1,1'-biphenyl substituents. Both mono- and bidentate phosphites are prepared in good yields. Two types of silsesquioxanes are employed as starting materials. The monophosphinite I and the monophosphite 2 are prepared from the thallium silsesquioxide derived from a completely condensed silsesquioxane framework (c-C5H9)(7)Si7O12SiOTl. The diphosphite 3 is synthesized starting with the incompletely condensed monosilylated disilanol (cC(5)H(9))(7)Si7O9(OSiMePh2)(OH)(2). For monophosphite 2, the corresponding trans- [PtCl2(2)] complex 4 is characterized by NMR spectroscopy as well as by Xray crystallography, as the first example of a completely condensed oxo-functionalized silsesquioxane framework. The coordination of the bidentate ligand 3 towards Pd, Mo and Rh is studied, both by NMR spectroscopy as well as by X-ray crystallography. Various modes of coordination are shown to be possible. The molecular structures for the complexes trans- [PdCl2(3)] (5), cis-[Mo(CO)(4)(3)] (6) and the dinuclear complex [{Rh( mu-Cl)(CO)}(2)(kappa(2)-3)] (7) have been determined. In the rhodium-catalyzed hydro-formylation of I-octene high activities, with turnover frequencies of up to 6800 h(-1), are obtained with these new nanosized phosphorus ligands.

Original language	English
Pages (from-to)	399-412
Number of pages	14
Journal	Advanced Synthesis & Catalysis
Volume	346
Issue number	4
DOIs	https://doi.org/10.1002/adsc.200303186
Publication status	Published - Mar-2004

Keywords

coordination chemistry
homogeneous catalysis
ligand design
phosphorus
silsesquioxanes
INCOMPLETELY-CONDENSED SILSESQUIOXANES
OLEFIN POLYMERIZATION CATALYSTS
SPEED EXPERIMENTATION TECHNIQUES
NANOFILTRATION MEMBRANE REACTOR
TRANSITION-METAL-COMPLEXES
SOLUBLE MODEL SYSTEMS
R1 = ME
POLYHEDRAL OLIGOSILSESQUIOXANES
EPOXIDATION CATALYSTS
COORDINATION CHEMISTRY

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Versatile phosphite ligands based on silsesquioxane backbones
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CCDC 220027: Experimental Crystal Structure Determination
Van Der Vlugt, J. I. (Contributor), Ackerstaff, J. (Contributor), Dijkstra, T. W. (Contributor), Mills, A. M. (Contributor), Kooijman, H. (Contributor), Spek, A. L. (Contributor), Meetsma, A. (Contributor), Abbenhuis, H. C. L. (Contributor) & Vogt, D. (Contributor), University of Groningen, 17-Sept-2003
DOI: 10.5517/cc7cyn5
Dataset
CCDC 220025: Experimental Crystal Structure Determination
Van Der Vlugt, J. I. (Contributor), Ackerstaff, J. (Contributor), Dijkstra, T. W. (Contributor), Mills, A. M. (Contributor), Kooijman, H. (Contributor), Spek, A. L. (Contributor), Meetsma, A. (Contributor), Abbenhuis, H. C. L. (Contributor) & Vogt, D. (Contributor), University of Groningen, 17-Sept-2003
DOI: 10.5517/cc7cyl3
Dataset
CCDC 220028: Experimental Crystal Structure Determination
Van Der Vlugt, J. I. (Contributor), Ackerstaff, J. (Contributor), Dijkstra, T. W. (Contributor), Mills, A. M. (Contributor), Kooijman, H. (Contributor), Spek, A. L. (Contributor), Meetsma, A. (Contributor), Abbenhuis, H. C. L. (Contributor) & Vogt, D. (Contributor), University of Groningen, 17-Sept-2003
DOI: 10.5517/cc7cyp6
Dataset

Cite this

@article{ba24616e531c4ff28e051802b77e3360,

title = "Versatile phosphite ligands based on silsesquioxane backbones",

abstract = "Silsesquioxanes are employed as ligand backbones for the synthesis of novel phosphite compounds with 3,3'-5,5'-tetrakis(tert-butyl)-2,2'-di-oxa-1,1'-biphenyl substituents. Both mono- and bidentate phosphites are prepared in good yields. Two types of silsesquioxanes are employed as starting materials. The monophosphinite I and the monophosphite 2 are prepared from the thallium silsesquioxide derived from a completely condensed silsesquioxane framework (c-C5H9)(7)Si7O12SiOTl. The diphosphite 3 is synthesized starting with the incompletely condensed monosilylated disilanol (cC(5)H(9))(7)Si7O9(OSiMePh2)(OH)(2). For monophosphite 2, the corresponding trans- [PtCl2(2)] complex 4 is characterized by NMR spectroscopy as well as by Xray crystallography, as the first example of a completely condensed oxo-functionalized silsesquioxane framework. The coordination of the bidentate ligand 3 towards Pd, Mo and Rh is studied, both by NMR spectroscopy as well as by X-ray crystallography. Various modes of coordination are shown to be possible. The molecular structures for the complexes trans- [PdCl2(3)] (5), cis-[Mo(CO)(4)(3)] (6) and the dinuclear complex [{Rh( mu-Cl)(CO)}(2)(kappa(2)-3)] (7) have been determined. In the rhodium-catalyzed hydro-formylation of I-octene high activities, with turnover frequencies of up to 6800 h(-1), are obtained with these new nanosized phosphorus ligands.",

keywords = "coordination chemistry, homogeneous catalysis, ligand design, phosphorus, silsesquioxanes, INCOMPLETELY-CONDENSED SILSESQUIOXANES, OLEFIN POLYMERIZATION CATALYSTS, SPEED EXPERIMENTATION TECHNIQUES, NANOFILTRATION MEMBRANE REACTOR, TRANSITION-METAL-COMPLEXES, SOLUBLE MODEL SYSTEMS, R1 = ME, POLYHEDRAL OLIGOSILSESQUIOXANES, EPOXIDATION CATALYSTS, COORDINATION CHEMISTRY",

author = "{van der Vlugt}, {J I} and J Ackerstaff and Dijkstra, {T W} and Mills, {A M} and H Kooijman and Spek, {A L} and A Meetsma and Abbenhuis, {H C L} and D Vogt",

year = "2004",

month = mar,

doi = "10.1002/adsc.200303186",

language = "English",

volume = "346",

pages = "399--412",

journal = "Advanced Synthesis & Catalysis",

issn = "1615-4150",

publisher = "WILEY-V C H VERLAG GMBH",

number = "4",

}

TY - JOUR

T1 - Versatile phosphite ligands based on silsesquioxane backbones

AU - van der Vlugt, J I

AU - Ackerstaff, J

AU - Dijkstra, T W

AU - Mills, A M

AU - Kooijman, H

AU - Spek, A L

AU - Meetsma, A

AU - Abbenhuis, H C L

AU - Vogt, D

PY - 2004/3

Y1 - 2004/3

N2 - Silsesquioxanes are employed as ligand backbones for the synthesis of novel phosphite compounds with 3,3'-5,5'-tetrakis(tert-butyl)-2,2'-di-oxa-1,1'-biphenyl substituents. Both mono- and bidentate phosphites are prepared in good yields. Two types of silsesquioxanes are employed as starting materials. The monophosphinite I and the monophosphite 2 are prepared from the thallium silsesquioxide derived from a completely condensed silsesquioxane framework (c-C5H9)(7)Si7O12SiOTl. The diphosphite 3 is synthesized starting with the incompletely condensed monosilylated disilanol (cC(5)H(9))(7)Si7O9(OSiMePh2)(OH)(2). For monophosphite 2, the corresponding trans- [PtCl2(2)] complex 4 is characterized by NMR spectroscopy as well as by Xray crystallography, as the first example of a completely condensed oxo-functionalized silsesquioxane framework. The coordination of the bidentate ligand 3 towards Pd, Mo and Rh is studied, both by NMR spectroscopy as well as by X-ray crystallography. Various modes of coordination are shown to be possible. The molecular structures for the complexes trans- [PdCl2(3)] (5), cis-[Mo(CO)(4)(3)] (6) and the dinuclear complex [{Rh( mu-Cl)(CO)}(2)(kappa(2)-3)] (7) have been determined. In the rhodium-catalyzed hydro-formylation of I-octene high activities, with turnover frequencies of up to 6800 h(-1), are obtained with these new nanosized phosphorus ligands.

AB - Silsesquioxanes are employed as ligand backbones for the synthesis of novel phosphite compounds with 3,3'-5,5'-tetrakis(tert-butyl)-2,2'-di-oxa-1,1'-biphenyl substituents. Both mono- and bidentate phosphites are prepared in good yields. Two types of silsesquioxanes are employed as starting materials. The monophosphinite I and the monophosphite 2 are prepared from the thallium silsesquioxide derived from a completely condensed silsesquioxane framework (c-C5H9)(7)Si7O12SiOTl. The diphosphite 3 is synthesized starting with the incompletely condensed monosilylated disilanol (cC(5)H(9))(7)Si7O9(OSiMePh2)(OH)(2). For monophosphite 2, the corresponding trans- [PtCl2(2)] complex 4 is characterized by NMR spectroscopy as well as by Xray crystallography, as the first example of a completely condensed oxo-functionalized silsesquioxane framework. The coordination of the bidentate ligand 3 towards Pd, Mo and Rh is studied, both by NMR spectroscopy as well as by X-ray crystallography. Various modes of coordination are shown to be possible. The molecular structures for the complexes trans- [PdCl2(3)] (5), cis-[Mo(CO)(4)(3)] (6) and the dinuclear complex [{Rh( mu-Cl)(CO)}(2)(kappa(2)-3)] (7) have been determined. In the rhodium-catalyzed hydro-formylation of I-octene high activities, with turnover frequencies of up to 6800 h(-1), are obtained with these new nanosized phosphorus ligands.

KW - coordination chemistry

KW - homogeneous catalysis

KW - ligand design

KW - phosphorus

KW - silsesquioxanes

KW - INCOMPLETELY-CONDENSED SILSESQUIOXANES

KW - OLEFIN POLYMERIZATION CATALYSTS

KW - SPEED EXPERIMENTATION TECHNIQUES

KW - NANOFILTRATION MEMBRANE REACTOR

KW - TRANSITION-METAL-COMPLEXES

KW - SOLUBLE MODEL SYSTEMS

KW - R1 = ME

KW - POLYHEDRAL OLIGOSILSESQUIOXANES

KW - EPOXIDATION CATALYSTS

KW - COORDINATION CHEMISTRY

U2 - 10.1002/adsc.200303186

DO - 10.1002/adsc.200303186

M3 - Review article

SN - 1615-4150

VL - 346

SP - 399

EP - 412

JO - Advanced Synthesis & Catalysis

JF - Advanced Synthesis & Catalysis

IS - 4

ER -

Versatile phosphite ligands based on silsesquioxane backbones

Abstract

Keywords

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Datasets

CCDC 220027: Experimental Crystal Structure Determination

CCDC 220025: Experimental Crystal Structure Determination

CCDC 220028: Experimental Crystal Structure Determination

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