Tantalum isocyanide complexes: Tai(CNDipp)6 (dipp is 2,6-diisopropylphenyl) and ionic [ta(CNDipp)7][ta(CNDipp)6], a formal disproportionation product of the 17-electron ta 0 metalloradical ta(CNDipp)6

William W. Brennessel, Alexander Romanenkov, Victor G Young, John E Ellis

Research output: Contribution to journalArticle

Abstract

Treatment of tetraethylammonium hexacarbonyltantalate, [Et 4 N][Ta(CO) 6 ], with 1.1 equivalents of molecular iodine (I 2 ) in tetrahydrofuran (THF) at 200 K, followed by the addition of 6.0 equivalents of 2,6-diisopropylphenyl isocyanide (CNDipp) and slow warming to 293 K over a 24 h period gave the tantalum(I) iodide derivative hexakis(2,6-diisopropylphenyl isocyanide-κC)iodidotantalum(I), [TaI(C 13 H 17 N) 6 ] or TaI(CNDipp) 6 , 1. Recrystallization of this substance from pentane provided deep-red nearly black parallelepipeds of the product, which was characterized by single-crystal X-ray diffraction. Addition of 1 in THF at 200 K to a suspension of an excess (5.8 equivalents) of caesium graphite (CsC 8 ), followed by warming, filtration, and solvent removal, afforded a dark-green oily solid of unknown composition, from which several red–brown rhombohedral plates of the ditantalum salt heptakis(2,6-diisopropylphenyl isocyanide-κC)tantalum hexakis(2,6-diisopropylphenyl isocyanide-κC)tantalate, [Ta(C 13 H 17 N) 7 ][Ta(C 13 H 17 N) 6 ] or [Ta(CNDipp) 7 ][Ta(CNDipp) 6 ], 2, were harvested. Salt 2 is a unique substance, as it is the only known example of a salt containing a homoleptic cation, [ML x ] + , and a homoleptic anion, [ML y ] , with the same transition metal and π-acceptor ligand L. In solution, 2 undergoes full comproportionation to afford the recently reported 17-electron paramagnetic zerovalent tantalum complex Ta(CNDipp) 6 , the only known isolable TaL 6 complex of Ta 0 .

Original languageEnglish (US)
Pages (from-to)135-140
Number of pages6
JournalActa Crystallographica Section C: Structural Chemistry
Volume75
DOIs
StatePublished - Jan 1 2019

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Tantalum
Cyanides
tantalum
Salts
tetrahydrofuran
salts
Electrons
products
parallelepipeds
heating
electrons
pentanes
Cesium
Iodine
cesium
iodides
iodine
Tetraethylammonium
Transition metals
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Keywords

  • 2,6-diisopropylphenyl
  • Crystal structure
  • Homoleptic
  • Isocyanide
  • Low valent
  • Monocapped trigonal prism
  • Seven-coordinate
  • Tantalum

PubMed: MeSH publication types

  • Journal Article

Cite this

@article{02246d1afcbc499cb8dee632c725f2ae,
title = "Tantalum isocyanide complexes: Tai(CNDipp)6 (dipp is 2,6-diisopropylphenyl) and ionic [ta(CNDipp)7][ta(CNDipp)6], a formal disproportionation product of the 17-electron ta 0 metalloradical ta(CNDipp)6",
abstract = "Treatment of tetraethylammonium hexacarbonyltantalate, [Et 4 N][Ta(CO) 6 ], with 1.1 equivalents of molecular iodine (I 2 ) in tetrahydrofuran (THF) at 200 K, followed by the addition of 6.0 equivalents of 2,6-diisopropylphenyl isocyanide (CNDipp) and slow warming to 293 K over a 24 h period gave the tantalum(I) iodide derivative hexakis(2,6-diisopropylphenyl isocyanide-κC)iodidotantalum(I), [TaI(C 13 H 17 N) 6 ] or TaI(CNDipp) 6 , 1. Recrystallization of this substance from pentane provided deep-red nearly black parallelepipeds of the product, which was characterized by single-crystal X-ray diffraction. Addition of 1 in THF at 200 K to a suspension of an excess (5.8 equivalents) of caesium graphite (CsC 8 ), followed by warming, filtration, and solvent removal, afforded a dark-green oily solid of unknown composition, from which several red–brown rhombohedral plates of the ditantalum salt heptakis(2,6-diisopropylphenyl isocyanide-κC)tantalum hexakis(2,6-diisopropylphenyl isocyanide-κC)tantalate, [Ta(C 13 H 17 N) 7 ][Ta(C 13 H 17 N) 6 ] or [Ta(CNDipp) 7 ][Ta(CNDipp) 6 ], 2, were harvested. Salt 2 is a unique substance, as it is the only known example of a salt containing a homoleptic cation, [ML x ] + , and a homoleptic anion, [ML y ] − , with the same transition metal and π-acceptor ligand L. In solution, 2 undergoes full comproportionation to afford the recently reported 17-electron paramagnetic zerovalent tantalum complex Ta(CNDipp) 6 , the only known isolable TaL 6 complex of Ta 0 .",
keywords = "2,6-diisopropylphenyl, Crystal structure, Homoleptic, Isocyanide, Low valent, Monocapped trigonal prism, Seven-coordinate, Tantalum",
author = "Brennessel, {William W.} and Alexander Romanenkov and Young, {Victor G} and Ellis, {John E}",
year = "2019",
month = "1",
day = "1",
doi = "10.1107/S2053229619000834",
language = "English (US)",
volume = "75",
pages = "135--140",
journal = "Acta crystallographica. Section C, Structural chemistry",
issn = "2053-2296",
publisher = "John Wiley and Sons Inc.",

}

TY - JOUR

T1 - Tantalum isocyanide complexes

T2 - Tai(CNDipp)6 (dipp is 2,6-diisopropylphenyl) and ionic [ta(CNDipp)7][ta(CNDipp)6], a formal disproportionation product of the 17-electron ta 0 metalloradical ta(CNDipp)6

AU - Brennessel, William W.

AU - Romanenkov, Alexander

AU - Young, Victor G

AU - Ellis, John E

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Treatment of tetraethylammonium hexacarbonyltantalate, [Et 4 N][Ta(CO) 6 ], with 1.1 equivalents of molecular iodine (I 2 ) in tetrahydrofuran (THF) at 200 K, followed by the addition of 6.0 equivalents of 2,6-diisopropylphenyl isocyanide (CNDipp) and slow warming to 293 K over a 24 h period gave the tantalum(I) iodide derivative hexakis(2,6-diisopropylphenyl isocyanide-κC)iodidotantalum(I), [TaI(C 13 H 17 N) 6 ] or TaI(CNDipp) 6 , 1. Recrystallization of this substance from pentane provided deep-red nearly black parallelepipeds of the product, which was characterized by single-crystal X-ray diffraction. Addition of 1 in THF at 200 K to a suspension of an excess (5.8 equivalents) of caesium graphite (CsC 8 ), followed by warming, filtration, and solvent removal, afforded a dark-green oily solid of unknown composition, from which several red–brown rhombohedral plates of the ditantalum salt heptakis(2,6-diisopropylphenyl isocyanide-κC)tantalum hexakis(2,6-diisopropylphenyl isocyanide-κC)tantalate, [Ta(C 13 H 17 N) 7 ][Ta(C 13 H 17 N) 6 ] or [Ta(CNDipp) 7 ][Ta(CNDipp) 6 ], 2, were harvested. Salt 2 is a unique substance, as it is the only known example of a salt containing a homoleptic cation, [ML x ] + , and a homoleptic anion, [ML y ] − , with the same transition metal and π-acceptor ligand L. In solution, 2 undergoes full comproportionation to afford the recently reported 17-electron paramagnetic zerovalent tantalum complex Ta(CNDipp) 6 , the only known isolable TaL 6 complex of Ta 0 .

AB - Treatment of tetraethylammonium hexacarbonyltantalate, [Et 4 N][Ta(CO) 6 ], with 1.1 equivalents of molecular iodine (I 2 ) in tetrahydrofuran (THF) at 200 K, followed by the addition of 6.0 equivalents of 2,6-diisopropylphenyl isocyanide (CNDipp) and slow warming to 293 K over a 24 h period gave the tantalum(I) iodide derivative hexakis(2,6-diisopropylphenyl isocyanide-κC)iodidotantalum(I), [TaI(C 13 H 17 N) 6 ] or TaI(CNDipp) 6 , 1. Recrystallization of this substance from pentane provided deep-red nearly black parallelepipeds of the product, which was characterized by single-crystal X-ray diffraction. Addition of 1 in THF at 200 K to a suspension of an excess (5.8 equivalents) of caesium graphite (CsC 8 ), followed by warming, filtration, and solvent removal, afforded a dark-green oily solid of unknown composition, from which several red–brown rhombohedral plates of the ditantalum salt heptakis(2,6-diisopropylphenyl isocyanide-κC)tantalum hexakis(2,6-diisopropylphenyl isocyanide-κC)tantalate, [Ta(C 13 H 17 N) 7 ][Ta(C 13 H 17 N) 6 ] or [Ta(CNDipp) 7 ][Ta(CNDipp) 6 ], 2, were harvested. Salt 2 is a unique substance, as it is the only known example of a salt containing a homoleptic cation, [ML x ] + , and a homoleptic anion, [ML y ] − , with the same transition metal and π-acceptor ligand L. In solution, 2 undergoes full comproportionation to afford the recently reported 17-electron paramagnetic zerovalent tantalum complex Ta(CNDipp) 6 , the only known isolable TaL 6 complex of Ta 0 .

KW - 2,6-diisopropylphenyl

KW - Crystal structure

KW - Homoleptic

KW - Isocyanide

KW - Low valent

KW - Monocapped trigonal prism

KW - Seven-coordinate

KW - Tantalum

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U2 - 10.1107/S2053229619000834

DO - 10.1107/S2053229619000834

M3 - Article

C2 - 30720451

AN - SCOPUS:85060619268

VL - 75

SP - 135

EP - 140

JO - Acta crystallographica. Section C, Structural chemistry

JF - Acta crystallographica. Section C, Structural chemistry

SN - 2053-2296

ER -