Regiospecific reactions of cobalt-rhodium mixed-metal clusters. Unprecedented, facile and reversible tetranuclear-dinuclear transformations involving diphenylacetylene and/or carbon monoxide

I. Horváth, László Zsolnai, Gottfried Huttner

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Abstract

Co2Rh2(CO)12 (1) reacts with alkynes (RC2R, R = C6F5 (2a), R = Ph (2b)) via specific insertion into the cobalt-cobalt bond to give Co2Rh2(CO)1042-RC2R) (3a,b). 3a was characterized by a single-crystal X-ray diffraction analysis: space group P21/c (No. 14), a = 11.286 (8) Å, b = 17.37 (1) Å, c = 16.65 (1) Å, β= 126.32 (5)°, V = 2630 (5) A7ring;3, Z = 4, Dcalcd, = 2.43 g/ cm3. A total of 2479 reflections (I ≥ 2σ) of 3215 reflections were used to give RF = 5.2% and RF2 = 5.6%. Reaction of 3a with CO and 2a results in regiospecific fragmentation to give CoRh(CO)6(μ-η2-F5C6C 2C6F5) (4a) exclusively. 3b undergoes facile, reversible, and regiospecific fragmentation when treated with PhC2Ph (2b) and carbon monoxide to give CoRh(CO)6(μ-η2-PhC2Ph) (4b). Medium-pressure in situ IR studies have revealed that 3b reacts with carbon monoxide in a reversible and regiospecific reaction to give the 1:1 mixture of CoRh(CO)7 (5) and 4b.

Original languageEnglish
Pages (from-to)180-182
Number of pages3
JournalOrganometallics
Volume5
Issue number1
Publication statusPublished - 1986

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Rhodium
metal clusters
Carbon Monoxide
Cobalt
rhodium
carbon monoxide
fragmentation
cobalt
Metals
Alkynes
alkynes
X ray diffraction analysis
insertion
Single crystals
single crystals
diffraction
x rays
biphenylacetylene

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

@article{6560c7aa363c4ec98e08fb80fdc8603a,
title = "Regiospecific reactions of cobalt-rhodium mixed-metal clusters. Unprecedented, facile and reversible tetranuclear-dinuclear transformations involving diphenylacetylene and/or carbon monoxide",
abstract = "Co2Rh2(CO)12 (1) reacts with alkynes (RC2R, R = C6F5 (2a), R = Ph (2b)) via specific insertion into the cobalt-cobalt bond to give Co2Rh2(CO)10(μ4-η 2-RC2R) (3a,b). 3a was characterized by a single-crystal X-ray diffraction analysis: space group P21/c (No. 14), a = 11.286 (8) {\AA}, b = 17.37 (1) {\AA}, c = 16.65 (1) {\AA}, β= 126.32 (5)°, V = 2630 (5) A7ring;3, Z = 4, Dcalcd, = 2.43 g/ cm3. A total of 2479 reflections (I ≥ 2σ) of 3215 reflections were used to give RF = 5.2{\%} and RF2 = 5.6{\%}. Reaction of 3a with CO and 2a results in regiospecific fragmentation to give CoRh(CO)6(μ-η2-F5C6C 2C6F5) (4a) exclusively. 3b undergoes facile, reversible, and regiospecific fragmentation when treated with PhC2Ph (2b) and carbon monoxide to give CoRh(CO)6(μ-η2-PhC2Ph) (4b). Medium-pressure in situ IR studies have revealed that 3b reacts with carbon monoxide in a reversible and regiospecific reaction to give the 1:1 mixture of CoRh(CO)7 (5) and 4b.",
author = "I. Horv{\'a}th and L{\'a}szl{\'o} Zsolnai and Gottfried Huttner",
year = "1986",
language = "English",
volume = "5",
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journal = "Organometallics",
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T1 - Regiospecific reactions of cobalt-rhodium mixed-metal clusters. Unprecedented, facile and reversible tetranuclear-dinuclear transformations involving diphenylacetylene and/or carbon monoxide

AU - Horváth, I.

AU - Zsolnai, László

AU - Huttner, Gottfried

PY - 1986

Y1 - 1986

N2 - Co2Rh2(CO)12 (1) reacts with alkynes (RC2R, R = C6F5 (2a), R = Ph (2b)) via specific insertion into the cobalt-cobalt bond to give Co2Rh2(CO)10(μ4-η 2-RC2R) (3a,b). 3a was characterized by a single-crystal X-ray diffraction analysis: space group P21/c (No. 14), a = 11.286 (8) Å, b = 17.37 (1) Å, c = 16.65 (1) Å, β= 126.32 (5)°, V = 2630 (5) A7ring;3, Z = 4, Dcalcd, = 2.43 g/ cm3. A total of 2479 reflections (I ≥ 2σ) of 3215 reflections were used to give RF = 5.2% and RF2 = 5.6%. Reaction of 3a with CO and 2a results in regiospecific fragmentation to give CoRh(CO)6(μ-η2-F5C6C 2C6F5) (4a) exclusively. 3b undergoes facile, reversible, and regiospecific fragmentation when treated with PhC2Ph (2b) and carbon monoxide to give CoRh(CO)6(μ-η2-PhC2Ph) (4b). Medium-pressure in situ IR studies have revealed that 3b reacts with carbon monoxide in a reversible and regiospecific reaction to give the 1:1 mixture of CoRh(CO)7 (5) and 4b.

AB - Co2Rh2(CO)12 (1) reacts with alkynes (RC2R, R = C6F5 (2a), R = Ph (2b)) via specific insertion into the cobalt-cobalt bond to give Co2Rh2(CO)10(μ4-η 2-RC2R) (3a,b). 3a was characterized by a single-crystal X-ray diffraction analysis: space group P21/c (No. 14), a = 11.286 (8) Å, b = 17.37 (1) Å, c = 16.65 (1) Å, β= 126.32 (5)°, V = 2630 (5) A7ring;3, Z = 4, Dcalcd, = 2.43 g/ cm3. A total of 2479 reflections (I ≥ 2σ) of 3215 reflections were used to give RF = 5.2% and RF2 = 5.6%. Reaction of 3a with CO and 2a results in regiospecific fragmentation to give CoRh(CO)6(μ-η2-F5C6C 2C6F5) (4a) exclusively. 3b undergoes facile, reversible, and regiospecific fragmentation when treated with PhC2Ph (2b) and carbon monoxide to give CoRh(CO)6(μ-η2-PhC2Ph) (4b). Medium-pressure in situ IR studies have revealed that 3b reacts with carbon monoxide in a reversible and regiospecific reaction to give the 1:1 mixture of CoRh(CO)7 (5) and 4b.

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