Structural characterization and coordination behavior of 1,2-diphosphino and 1,2-diarsino-diborane(4) compounds

Afarin Moezzi; Marilyn M. Olmstead; Doris C. Pestana; Karin Ruhlandt; Philip P. Power

doi:10.1080/13583149612331338435

Structural characterization and coordination behavior of 1,2-diphosphino and 1,2-diarsino-diborane(4) compounds

Afarin Moezzi, Marilyn M. Olmstead, Doris C. Pestana, Karin Ruhlandt, Philip P. Power

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

2 Scopus citations

Abstract

Reaction of either LiPPh₂ or LiAsMes₂ with the diborane(4) compound (Me₂N) BrBBBr(NMe₂) affords the compounds (Me₂N)(Ph₂P)BB(PPh₂)(NMe₂), 1, and (Me₂N) (Mes₂As)BB(AsMes₂)(NMe₂)-0.5PhMe, 2-0.5PhMe (Mes = 2,4,6-Me₃C₆H₂-). Both 1 and 2 feature normal B-B single bond lengths; However, the empty boron p-orbitals display strong π-interactions with the dimethylamino substituents. The B-P and B-As distances and the pyramidal phosphorus and arsenic geometries are consistent with single bonding. Furthermore, the stereochemical activity of the phosphorus and arsenic lone pairs is demonstrated by the ready formation of the complex cis-[Cr(CO)₄(Me₂N)(Ph₂P) BB(PPh₂)(NMe₂)] C₆H₆, 3-C₆H₆, by treatment of 1 with [Cr(CO)₄(2,5-norbornadiene)]. Compounds 1-3 were characterized by X-ray crystallography, nB and 31P NMR spectroscopy, and by IR spectroscopy in the case of 3.

Original language	English (US)
Pages (from-to)	197-206
Number of pages	10
Journal	Main Group Chemistry
Volume	1
Issue number	2
DOIs	https://doi.org/10.1080/13583149612331338435
State	Published - 1996
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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@article{88ccde2e22a34a7c89721e871cf74354,

title = "Structural characterization and coordination behavior of 1,2-diphosphino and 1,2-diarsino-diborane(4) compounds",

abstract = "Reaction of either LiPPh2 or LiAsMes2 with the diborane(4) compound (Me2N) BrBBBr(NMe2) affords the compounds (Me2N)(Ph2P)BB(PPh2)(NMe2), 1, and (Me2N) (Mes2As)BB(AsMes2)(NMe2)-0.5PhMe, 2-0.5PhMe (Mes = 2,4,6-Me3C6H2-). Both 1 and 2 feature normal B-B single bond lengths; However, the empty boron p-orbitals display strong π-interactions with the dimethylamino substituents. The B-P and B-As distances and the pyramidal phosphorus and arsenic geometries are consistent with single bonding. Furthermore, the stereochemical activity of the phosphorus and arsenic lone pairs is demonstrated by the ready formation of the complex cis-[Cr(CO)4(Me2N)(Ph2P) BB(PPh2)(NMe2)] C6H6, 3-C6H6, by treatment of 1 with [Cr(CO)4(2,5-norbornadiene)]. Compounds 1-3 were characterized by X-ray crystallography, nB and 31P NMR spectroscopy, and by IR spectroscopy in the case of 3.",

author = "Afarin Moezzi and Olmstead, {Marilyn M.} and Pestana, {Doris C.} and Karin Ruhlandt and Power, {Philip P.}",

year = "1996",

doi = "10.1080/13583149612331338435",

language = "English (US)",

volume = "1",

pages = "197--206",

journal = "Main Group Chemistry",

issn = "1024-1221",

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TY - JOUR

T1 - Structural characterization and coordination behavior of 1,2-diphosphino and 1,2-diarsino-diborane(4) compounds

AU - Moezzi, Afarin

AU - Olmstead, Marilyn M.

AU - Pestana, Doris C.

AU - Ruhlandt, Karin

AU - Power, Philip P.

PY - 1996

Y1 - 1996

N2 - Reaction of either LiPPh2 or LiAsMes2 with the diborane(4) compound (Me2N) BrBBBr(NMe2) affords the compounds (Me2N)(Ph2P)BB(PPh2)(NMe2), 1, and (Me2N) (Mes2As)BB(AsMes2)(NMe2)-0.5PhMe, 2-0.5PhMe (Mes = 2,4,6-Me3C6H2-). Both 1 and 2 feature normal B-B single bond lengths; However, the empty boron p-orbitals display strong π-interactions with the dimethylamino substituents. The B-P and B-As distances and the pyramidal phosphorus and arsenic geometries are consistent with single bonding. Furthermore, the stereochemical activity of the phosphorus and arsenic lone pairs is demonstrated by the ready formation of the complex cis-[Cr(CO)4(Me2N)(Ph2P) BB(PPh2)(NMe2)] C6H6, 3-C6H6, by treatment of 1 with [Cr(CO)4(2,5-norbornadiene)]. Compounds 1-3 were characterized by X-ray crystallography, nB and 31P NMR spectroscopy, and by IR spectroscopy in the case of 3.

AB - Reaction of either LiPPh2 or LiAsMes2 with the diborane(4) compound (Me2N) BrBBBr(NMe2) affords the compounds (Me2N)(Ph2P)BB(PPh2)(NMe2), 1, and (Me2N) (Mes2As)BB(AsMes2)(NMe2)-0.5PhMe, 2-0.5PhMe (Mes = 2,4,6-Me3C6H2-). Both 1 and 2 feature normal B-B single bond lengths; However, the empty boron p-orbitals display strong π-interactions with the dimethylamino substituents. The B-P and B-As distances and the pyramidal phosphorus and arsenic geometries are consistent with single bonding. Furthermore, the stereochemical activity of the phosphorus and arsenic lone pairs is demonstrated by the ready formation of the complex cis-[Cr(CO)4(Me2N)(Ph2P) BB(PPh2)(NMe2)] C6H6, 3-C6H6, by treatment of 1 with [Cr(CO)4(2,5-norbornadiene)]. Compounds 1-3 were characterized by X-ray crystallography, nB and 31P NMR spectroscopy, and by IR spectroscopy in the case of 3.

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Structural characterization and coordination behavior of 1,2-diphosphino and 1,2-diarsino-diborane(4) compounds

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