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Title: Chemistry of the hexaborane(10) analogue (PPh{sub 3}){sub 2}(CO)IrB{sub 5}H{sub 8}: Formation and characterization of the heterobimetallaheptaboranes 1,1,1-(CO){sub 3}-2,2-(CO){sub 2}-2,4-(PPh{sub 3}){sub 2-closo-}-1,2-FeIrB{sub 5}H{sub 4} and 2-(CO)-2,2-(PPh{sub 3}){sub 2}-7-Cl-7-(PMe{sub 2}Ph)-nido-2,7-IrPtB{sub 5}H{sub 7}

Abstract

The chemistry of the hexaborane(10) analogue (PPh{sub 3}){sub 2}(CO)IrB{sub 5}H{sub 8} (4) has been investigated. The two standard reactions in which metal-containing moieties may be incorporated into the B{sub 6}H{sub 10} cage find success when applied to the iridahexaborane (4). The reaction of Fe{sub 2}(CO){sub 9} with (PPh{sub 3}){sub 2}(CO)IrB{sub 5}H{sub 8} in C{sub 6}H{sub 6} solution affords 1,1,1-(CO){sub 3}-2,2-(CO){sub 2}-2,4-(PPh{sub 3}){sub 2-closo}-1,2-FeIrB{sub 5}H{sub 4} (1) in moderate (28.5%) yield. Except for carborane derivatives, 1 is the first pentagonal bipyramidal metallaheptaborane to be structurally characterized. Compound 1 was identified by NMR, IR, and high-resolution mass spectroscopy and by a single-crystal X-ray diffraction study. Treatment of a THF solution of the sodium anion salt of 4, Na[(PPh{sub 3}){sub 2}(CO)IrB{sub 5}H{sub 7}], with [Pt(PMe{sub 2}Ph)Cl{sub 2}]{sub 2} in Ch{sub 2}Cl{sub 2} affords yellow solid 2-(CO)-2,2-(PPh{sub 3}){sub 2}-7-Cl-7-(PM3{sub 2}-Ph)-nido-2,7-IrPtB{sub 5}H{sub 7} (2) in 5% yield. 2 is identified similarily. It exists as a nido seven-vertex cluster formally derived by removal of a vertex of connectivity 5 from a closed triangulated dodecahedral polyhedron. 2 is two skeletal electrons short of the electron count for a classical nido cluster, and it is compared to systems with related structures and also to other systems containing themore » Pt moiety functioning as a two-orbital two-electon donor.« less

Authors:
; ; ;  [1]
  1. Univ. of Missouri, St. Louis, MO (United States)
Publication Date:
OSTI Identifier:
263754
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 35; Journal Issue: 7; Other Information: PBD: 27 Mar 1996
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; IRIDIUM COMPOUNDS; STRUCTURAL CHEMICAL ANALYSIS; CHEMICAL REACTIONS; BORANES; CHEMICAL REACTION YIELD; NUCLEAR MAGNETIC RESONANCE; ABSORPTION SPECTROSCOPY; MASS SPECTROSCOPY

Citation Formats

Bould, J, Rath, N P, Fang, H, and Barton, L. Chemistry of the hexaborane(10) analogue (PPh{sub 3}){sub 2}(CO)IrB{sub 5}H{sub 8}: Formation and characterization of the heterobimetallaheptaboranes 1,1,1-(CO){sub 3}-2,2-(CO){sub 2}-2,4-(PPh{sub 3}){sub 2-closo-}-1,2-FeIrB{sub 5}H{sub 4} and 2-(CO)-2,2-(PPh{sub 3}){sub 2}-7-Cl-7-(PMe{sub 2}Ph)-nido-2,7-IrPtB{sub 5}H{sub 7}. United States: N. p., 1996. Web. doi:10.1021/ic951165p.
Bould, J, Rath, N P, Fang, H, & Barton, L. Chemistry of the hexaborane(10) analogue (PPh{sub 3}){sub 2}(CO)IrB{sub 5}H{sub 8}: Formation and characterization of the heterobimetallaheptaboranes 1,1,1-(CO){sub 3}-2,2-(CO){sub 2}-2,4-(PPh{sub 3}){sub 2-closo-}-1,2-FeIrB{sub 5}H{sub 4} and 2-(CO)-2,2-(PPh{sub 3}){sub 2}-7-Cl-7-(PMe{sub 2}Ph)-nido-2,7-IrPtB{sub 5}H{sub 7}. United States. doi:10.1021/ic951165p.
Bould, J, Rath, N P, Fang, H, and Barton, L. Wed . "Chemistry of the hexaborane(10) analogue (PPh{sub 3}){sub 2}(CO)IrB{sub 5}H{sub 8}: Formation and characterization of the heterobimetallaheptaboranes 1,1,1-(CO){sub 3}-2,2-(CO){sub 2}-2,4-(PPh{sub 3}){sub 2-closo-}-1,2-FeIrB{sub 5}H{sub 4} and 2-(CO)-2,2-(PPh{sub 3}){sub 2}-7-Cl-7-(PMe{sub 2}Ph)-nido-2,7-IrPtB{sub 5}H{sub 7}". United States. doi:10.1021/ic951165p.
@article{osti_263754,
title = {Chemistry of the hexaborane(10) analogue (PPh{sub 3}){sub 2}(CO)IrB{sub 5}H{sub 8}: Formation and characterization of the heterobimetallaheptaboranes 1,1,1-(CO){sub 3}-2,2-(CO){sub 2}-2,4-(PPh{sub 3}){sub 2-closo-}-1,2-FeIrB{sub 5}H{sub 4} and 2-(CO)-2,2-(PPh{sub 3}){sub 2}-7-Cl-7-(PMe{sub 2}Ph)-nido-2,7-IrPtB{sub 5}H{sub 7}},
author = {Bould, J and Rath, N P and Fang, H and Barton, L},
abstractNote = {The chemistry of the hexaborane(10) analogue (PPh{sub 3}){sub 2}(CO)IrB{sub 5}H{sub 8} (4) has been investigated. The two standard reactions in which metal-containing moieties may be incorporated into the B{sub 6}H{sub 10} cage find success when applied to the iridahexaborane (4). The reaction of Fe{sub 2}(CO){sub 9} with (PPh{sub 3}){sub 2}(CO)IrB{sub 5}H{sub 8} in C{sub 6}H{sub 6} solution affords 1,1,1-(CO){sub 3}-2,2-(CO){sub 2}-2,4-(PPh{sub 3}){sub 2-closo}-1,2-FeIrB{sub 5}H{sub 4} (1) in moderate (28.5%) yield. Except for carborane derivatives, 1 is the first pentagonal bipyramidal metallaheptaborane to be structurally characterized. Compound 1 was identified by NMR, IR, and high-resolution mass spectroscopy and by a single-crystal X-ray diffraction study. Treatment of a THF solution of the sodium anion salt of 4, Na[(PPh{sub 3}){sub 2}(CO)IrB{sub 5}H{sub 7}], with [Pt(PMe{sub 2}Ph)Cl{sub 2}]{sub 2} in Ch{sub 2}Cl{sub 2} affords yellow solid 2-(CO)-2,2-(PPh{sub 3}){sub 2}-7-Cl-7-(PM3{sub 2}-Ph)-nido-2,7-IrPtB{sub 5}H{sub 7} (2) in 5% yield. 2 is identified similarily. It exists as a nido seven-vertex cluster formally derived by removal of a vertex of connectivity 5 from a closed triangulated dodecahedral polyhedron. 2 is two skeletal electrons short of the electron count for a classical nido cluster, and it is compared to systems with related structures and also to other systems containing the Pt moiety functioning as a two-orbital two-electon donor.},
doi = {10.1021/ic951165p},
journal = {Inorganic Chemistry},
number = 7,
volume = 35,
place = {United States},
year = {1996},
month = {3}
}