PMID- 23088762
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20130301
LR  - 20121105
IS  - 1520-510X (Electronic)
IS  - 0020-1669 (Linking)
VI  - 51
IP  - 21
DP  - 2012 Nov 5
TI  - Elucidating the mechanism of the halide-induced ligand rearrangement reaction.
PG  - 11986-95
LID - 10.1021/ic3018776 [doi]
AB  - The formation of heteroligated Rh(I) complexes containing two different 
      hemilabile phosphinoalkyl ligands, 
      (kappa(2)-Ph(2)PCH(2)CH(2)S-Aryl)(kappa(1)-Ph(2)PCH(2)CH(2)O-C(6)H(5))RhCl, through a 
      halide-induced ligand rearrangement (HILR) reaction has been studied 
      mechanistically. The half-life of this rearrangement reaction depends heavily on 
      the Rh(I) precursor used and the chelating ability of the phosphinoalkyl 
      thioether (PS) ligand, while the chelating ability of the phosphinoalkyl ether 
      (PO) ligand has less of an effect. An intermediate complex which contains two PO 
      ligands, (nbd)(kappa(1)-Ph(2)PCH(2)CH(2)O-C(6)H(5))(2)RhCl (nbd = norbornadiene), 
      converts to (nbd)(kappa(1)-Ph(2)PCH(2)CH(2)O-C(6)H(5))RhCl resulting in a free PO 
      ligand. The free PO ligand can then react with a homoligated PS complex 
      [(kappa(2)-Ph(2)PCH(2)CH(2)S-Aryl)(2)Rh](+)Cl(-) producing the heteroligated product. 
      The PS ligand generated during the reaction pathway can be trapped by the 
      monoligated PO complex (nbd)(kappa(1)-Ph(2)PCH(2)CH(2)O-C(6)H(5))RhCl, leading to the 
      formation of the same heteroligated product. In this study, some of the key 
      intermediates and reaction steps underlying the HILR reaction have been 
      identified by variable temperature (31)P(1)H NMR spectroscopy and in two cases 
      by single-crystal X-ray diffraction studies. Significantly, this work provides 
      mechanistic insight into the HILR process, which is a key reaction used to 
      prepare a large class of highly sophisticated three-dimensional 
      metallosupramolecular architectures and allosteric catalysts.
FAU - Yoo, Hyojong
AU  - Yoo H
AD  - Department of Chemistry and the International Institute for Nanotechnology, 
      Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA.
FAU - Rosen, Mari S
AU  - Rosen MS
FAU - Brown, Aaron M
AU  - Brown AM
FAU - Wiester, Michael J
AU  - Wiester MJ
FAU - Stern, Charlotte L
AU  - Stern CL
FAU - Mirkin, Chad A
AU  - Mirkin CA
LA  - eng
PT  - Journal Article
DEP - 20121022
PL  - United States
TA  - Inorg Chem
JT  - Inorganic chemistry
JID - 0366543
EDAT- 2012/10/24 06:00
MHDA- 2012/10/24 06:01
CRDT- 2012/10/24 06:00
PHST- 2012/10/24 06:00 [entrez]
PHST- 2012/10/24 06:00 [pubmed]
PHST- 2012/10/24 06:01 [medline]
AID - 10.1021/ic3018776 [doi]
PST - ppublish
SO  - Inorg Chem. 2012 Nov 5;51(21):11986-95. doi: 10.1021/ic3018776. Epub 2012 Oct 22.