pi effects involving Rh-PZ(3) compounds. The quantitative analysis of ligand effects (QALE)

M R  Wilson; A  Prock; W P  Giering; A L  Fernandez; C M  Haar; Steven Patrick Nolan; B M  Foxman

doi:10.1021/om011035q

pi effects involving Rh-PZ(3) compounds. The quantitative analysis of ligand effects (QALE)

M R Wilson, A Prock, W P Giering, A L Fernandez, C M Haar, Steven Patrick Nolan, B M Foxman

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

Abstract

Through the quantitative analysis of ligand effects (QALE), we have probed pi effects associated with Rh-P bond lengths, nu(CO), and -DeltaH(rx) for Rh(CO)(Cl)(PX3)(2) and nu(CO) and -DeltaH(rx) for Rh(acac)(CO)(PZ(3)). It was found that pi effects are complex and depend strongly on the nature of ancillary or other participatory groups. The results of the QALE analysis of -DeltaH(rx) point out the importance of synergistic interactions between PZ3 and other ancillary ligands in accord with theoretical computations. Literature data for Rh(CO)(Cl)(PZ3)2 have been supplemented with new values of DeltaH(rx) for PMe3 (-75.6 +/- 0.3 kcal/mol), P(i-Pr)(3) (-68.7 +/- 0.3 kcal/mol), and PCy3 (-66.4 +/- 0.4 kcal/mol) as well as crystal structures for Rh(CO)(Cl)(P(i-Pr-3))(2) (Rh-P = 2.34880 Angstrom) and Rh(CO)(Cl)(PCy3)(2) (Rh-P = 2.3508(3)).

Original language	English
Pages (from-to)	2758-2763
Number of pages	6
Journal	Organometallics
Volume	21
Issue number	13
DOIs	https://doi.org/10.1021/om011035q
Publication status	Published - 24 Jun 2002

Keywords

TERTIARY PHOSPHINE LIGAND
N-PYRROLYL PHOSPHINES
STEREOELECTRONIC PARAMETERS
REORGANIZATION ENERGIES
SUBSTITUTION-REACTIONS
ACCEPTOR CHARACTER
COMPLEXES
RHODIUM
BOND
CRYSTAL

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title = "pi effects involving Rh-PZ(3) compounds. The quantitative analysis of ligand effects (QALE)",

abstract = "Through the quantitative analysis of ligand effects (QALE), we have probed pi effects associated with Rh-P bond lengths, nu(CO), and -DeltaH(rx) for Rh(CO)(Cl)(PX3)(2) and nu(CO) and -DeltaH(rx) for Rh(acac)(CO)(PZ(3)). It was found that pi effects are complex and depend strongly on the nature of ancillary or other participatory groups. The results of the QALE analysis of -DeltaH(rx) point out the importance of synergistic interactions between PZ3 and other ancillary ligands in accord with theoretical computations. Literature data for Rh(CO)(Cl)(PZ3)2 have been supplemented with new values of DeltaH(rx) for PMe3 (-75.6 +/- 0.3 kcal/mol), P(i-Pr)(3) (-68.7 +/- 0.3 kcal/mol), and PCy3 (-66.4 +/- 0.4 kcal/mol) as well as crystal structures for Rh(CO)(Cl)(P(i-Pr-3))(2) (Rh-P = 2.34880 Angstrom) and Rh(CO)(Cl)(PCy3)(2) (Rh-P = 2.3508(3)).",

keywords = "TERTIARY PHOSPHINE LIGAND, N-PYRROLYL PHOSPHINES, STEREOELECTRONIC PARAMETERS, REORGANIZATION ENERGIES, SUBSTITUTION-REACTIONS, ACCEPTOR CHARACTER, COMPLEXES, RHODIUM, BOND, CRYSTAL",

author = "Wilson, {M R} and A Prock and Giering, {W P} and Fernandez, {A L} and Haar, {C M} and Nolan, {Steven Patrick} and Foxman, {B M}",

year = "2002",

month = jun,

day = "24",

doi = "10.1021/om011035q",

language = "English",

volume = "21",

pages = "2758--2763",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society (ACS)",

number = "13",

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TY - JOUR

T1 - pi effects involving Rh-PZ(3) compounds. The quantitative analysis of ligand effects (QALE)

AU - Wilson, M R

AU - Prock, A

AU - Giering, W P

AU - Fernandez, A L

AU - Haar, C M

AU - Nolan, Steven Patrick

AU - Foxman, B M

PY - 2002/6/24

Y1 - 2002/6/24

N2 - Through the quantitative analysis of ligand effects (QALE), we have probed pi effects associated with Rh-P bond lengths, nu(CO), and -DeltaH(rx) for Rh(CO)(Cl)(PX3)(2) and nu(CO) and -DeltaH(rx) for Rh(acac)(CO)(PZ(3)). It was found that pi effects are complex and depend strongly on the nature of ancillary or other participatory groups. The results of the QALE analysis of -DeltaH(rx) point out the importance of synergistic interactions between PZ3 and other ancillary ligands in accord with theoretical computations. Literature data for Rh(CO)(Cl)(PZ3)2 have been supplemented with new values of DeltaH(rx) for PMe3 (-75.6 +/- 0.3 kcal/mol), P(i-Pr)(3) (-68.7 +/- 0.3 kcal/mol), and PCy3 (-66.4 +/- 0.4 kcal/mol) as well as crystal structures for Rh(CO)(Cl)(P(i-Pr-3))(2) (Rh-P = 2.34880 Angstrom) and Rh(CO)(Cl)(PCy3)(2) (Rh-P = 2.3508(3)).

AB - Through the quantitative analysis of ligand effects (QALE), we have probed pi effects associated with Rh-P bond lengths, nu(CO), and -DeltaH(rx) for Rh(CO)(Cl)(PX3)(2) and nu(CO) and -DeltaH(rx) for Rh(acac)(CO)(PZ(3)). It was found that pi effects are complex and depend strongly on the nature of ancillary or other participatory groups. The results of the QALE analysis of -DeltaH(rx) point out the importance of synergistic interactions between PZ3 and other ancillary ligands in accord with theoretical computations. Literature data for Rh(CO)(Cl)(PZ3)2 have been supplemented with new values of DeltaH(rx) for PMe3 (-75.6 +/- 0.3 kcal/mol), P(i-Pr)(3) (-68.7 +/- 0.3 kcal/mol), and PCy3 (-66.4 +/- 0.4 kcal/mol) as well as crystal structures for Rh(CO)(Cl)(P(i-Pr-3))(2) (Rh-P = 2.34880 Angstrom) and Rh(CO)(Cl)(PCy3)(2) (Rh-P = 2.3508(3)).

KW - TERTIARY PHOSPHINE LIGAND

KW - N-PYRROLYL PHOSPHINES

KW - STEREOELECTRONIC PARAMETERS

KW - REORGANIZATION ENERGIES

KW - SUBSTITUTION-REACTIONS

KW - ACCEPTOR CHARACTER

KW - COMPLEXES

KW - RHODIUM

KW - BOND

KW - CRYSTAL

U2 - 10.1021/om011035q

DO - 10.1021/om011035q

M3 - Article

SN - 0276-7333

VL - 21

SP - 2758

EP - 2763

JO - Organometallics

JF - Organometallics

IS - 13

ER -

pi effects involving Rh-PZ(3) compounds. The quantitative analysis of ligand effects (QALE)

Abstract

Keywords

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