TY - JOUR
T1 - Synthesis and Structures of Compounds Containing Double Bonds Between the Heavier Group VA Elements
T2 - Diphosphenes, Diarsenes, Phosphaarsenes, And Phosphastibenes
AU - Cowley, Alan H.
AU - Kilduff, Jan E.
AU - Lasch, Jon G.
AU - Mehrotra, Sushil K.
AU - Norman, Nichlas C.
AU - Pakulski, Marek
AU - Whittlesey, Bruce R.
AU - Atwood, Jerry L.
AU - Hunter, William E.
PY - 1984/8
Y1 - 1984/8
N2 - The syntheses of the symmetrical diphosphene (Me3Si)3CP=PC(SiMe3)3 (2), the unsymmetrical diphosphenes [2,4,6-(t-Bu)3C6H2]P=PC(SiMe3)3 (5) and [2,4,6-(i-Bu)3C6H2]P=PCH(SiMe3)2 (7), the phosphaarsene [2,4,6-(ZBu)3C6H2]P=AsCH(SiMe3)2 (12), the phosphastibene [2,4,6-(f-Bu)3C6H2]P==SbCH(SiMe3)2 (14), and the diarsene [2,4,6-(z-Bu)3C6H2] As=AsCH(SiMe3)2 (18) are described. X-ray diffraction studies have been performed on 2,12, and 18. Diphosphene 2 crystallizes in space group Pi (No. 2) with a = 15.629 (7) Å, b = 9.155 (5) Å, c = 12.486 (6) Å, a = 91.58 (4)°, β = 111.42 (5)°, and y = 90.02 (4)°. Phosphaarsene 12 crystallizes in space group PI (No. 2) with a = 9.991 (4) k, b = 10.452 (9) Å, c = 15.140 (15) Å, a = 89.72 (7)°, β = 85.03 (5)°, and y = 77.72 (5)°. Diarsene 18 crystallizes in space group PI (No. 2) with a = 9.955 (9) Å, b = 10.393 (7) Å, c = 15.159 (5) Å, a = 89.56 (4)°, β = 85.39 (6)°, and y = 78.31 (9)°. The nature of the bonding in these and related double-bonded compounds is discussed with use of the available molecular structural and electronic spectral information. An extensive compilation of 31P NMR spectroscopic data is presented and discussed.
AB - The syntheses of the symmetrical diphosphene (Me3Si)3CP=PC(SiMe3)3 (2), the unsymmetrical diphosphenes [2,4,6-(t-Bu)3C6H2]P=PC(SiMe3)3 (5) and [2,4,6-(i-Bu)3C6H2]P=PCH(SiMe3)2 (7), the phosphaarsene [2,4,6-(ZBu)3C6H2]P=AsCH(SiMe3)2 (12), the phosphastibene [2,4,6-(f-Bu)3C6H2]P==SbCH(SiMe3)2 (14), and the diarsene [2,4,6-(z-Bu)3C6H2] As=AsCH(SiMe3)2 (18) are described. X-ray diffraction studies have been performed on 2,12, and 18. Diphosphene 2 crystallizes in space group Pi (No. 2) with a = 15.629 (7) Å, b = 9.155 (5) Å, c = 12.486 (6) Å, a = 91.58 (4)°, β = 111.42 (5)°, and y = 90.02 (4)°. Phosphaarsene 12 crystallizes in space group PI (No. 2) with a = 9.991 (4) k, b = 10.452 (9) Å, c = 15.140 (15) Å, a = 89.72 (7)°, β = 85.03 (5)°, and y = 77.72 (5)°. Diarsene 18 crystallizes in space group PI (No. 2) with a = 9.955 (9) Å, b = 10.393 (7) Å, c = 15.159 (5) Å, a = 89.56 (4)°, β = 85.39 (6)°, and y = 78.31 (9)°. The nature of the bonding in these and related double-bonded compounds is discussed with use of the available molecular structural and electronic spectral information. An extensive compilation of 31P NMR spectroscopic data is presented and discussed.
UR - http://www.scopus.com/inward/record.url?scp=33845469331&partnerID=8YFLogxK
U2 - 10.1021/ic00185a010
DO - 10.1021/ic00185a010
M3 - Article
AN - SCOPUS:33845469331
SN - 0020-1669
VL - 23
SP - 2582
EP - 2593
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 17
ER -