Angewandte
Chemie
[3] D. Gudat,A. Haghverdi,H. Hupfer,M. Nieger, Chem. Eur. J.
ogies to the recently reported “non-oxidative” insertion of a
2000, 6,3414.
À
metal atom into the P C bond of a phosphenium–carbene
adduct.[23]
[4] X. Sava,L. Ricard,F. Mathey,P. Le Floch,
2003, 350,182.
Inorg. Chim. Acta
Remarkably,unlike tetraaminodiphosphanes that may
[5] AVT-NMR study showed a significant temperature dependence
of the values of 1JP,P in 5a,b (5a: 1JP,P = 255 Hz (203 K) to 264 Hz
(363 K); 5b: 1JP,P = 177 Hz (203 K) to 204 Hz (363 K)). The
precise origin of this effect,which is likewise known for other
diphosphanes and has been explained by temperature-depend-
ent equilibria between conformers (cf. J. G. Verkade,L. D. Quin,
P-31 NMR-Spectroscopy in Stereochemical Analysis,VCH,
Deerfield Beach, 1987,p. 450f),is currently being intensively
investigated.
easily decay into two phosphanyl radicals,[24] 5a,b fail to react
À
with P4 under addition to a P P bond even in boiling toluene;
possibly,this may indicate a certain complementary nature of
reactions involving radical (R2P··PR2) or ionic (R2P+ ÀPR2)
À
activation of a P P bond.
In summary,we have described the synthesis and charac-
À
terization of diphosphanes with a polarized P P bond. The
molecules display not only an interesting bonding situation,
but also allow a variety of synthetically valuable transforma-
tions which are,together with coordination chemical studies,
currently under investigation.
[6] Crystal structure analyses: Nonius KappaCCD diffractometer,
T= 123(2) K,Mo
radiation (l = 0.71073 ),SHELX97 pro-
Ka
gram package[7] for structure solution (direct methods) and
refinement (full-matrix,least-squares refined against F2). The
positions of the hydrogen atoms were refined with a riding
model. 5a: yellow crystals,C 32H34N2P2, Mr = 508.6,crystal size
¯
0.45 0.30 0.20 mm,triclinic,space group
P1 (no. 2), a =
Experimental Section
8.1758(2), b = 10.6220(3), c = 17.1208(7) , a = 96. 601(2), b =
100.350(2), g = 106.349(2)8, V= 1381.75(8) 3, Z = 2, m(MoKa) =
0.181 mmÀ1, T= 123(2) K, F(000) = 540, qmax = 258,10884 reflec-
tions,of which 4866 were independent ( Rint = 0.043), R1 = 0.039
(for I > 2s(I)),w R2 = 0.089 (all data). 5b: yellow crystals,
C32H44N2P2, Mr = 518.6,crystal size 0.50 0.40 0.30 mm,tri-
5a,b: A solution of LiPPh2 (10 mmol) in THF (20 mL) or LiPC4Et4
(10 mmol)[4] in THF (50 mL) was added dropwise to a cooled
(À788C) solution of 4 (10 mmol) in THF (100 mL). The mixture was
then allowed to warm to ambient temperature,and stirred for one
additional hour. The solvent was removed in vacuum,the residue
extracted with hexane (100 mL),and filtered over Celite. The filtrate
was concentrated to 30 mL,and the product crystallized at À208C.
5a: M.p. 1938C,yield 77%. 1H NMR (C6D6): d = 7.22 (m,4H, o-
¯
clinic,space group P1 (no. 2), a = 8.1305(2), b = 8.9507(2), c =
20.5590(5) , a = 96.269(1), b = 90.165(1), g = 94.510(1)8, V=
1482.50(6) 3, Z = 2, m(MoKa) = 0.169 mmÀ1
,
F(000) = 560,
H
Ph),6.80–6.77 (m,6H, m/p-HPh),6.61 (br,4H, m-HMes),5.78 (d,2H,
qmax = 258; 13028 reflections,of which 5220 were independent
(Rint = 0.034); R1 = 0.044 (for I > 2s(I)),w R2 = 0.125 (all data).
CCDC-232847 (5a) and CCDC-232848 (5b) contain the supple-
mentary crystallographic data for this paper. These data can be
ving.html (or from the Cambridge Crystallographic Data Centre,
12,Union Road,Cambridge CB21EZ,UK; fax: ( + 44)1223-
336-033; or deposit@ccdc.cam.ac.uk).
3JP,H = 1.5 Hz,N-CH),2.40 (br,12H,
o-CH3),2.07 ppm (s,6H, p-
CH3); 13C{1H} NMR (C6D6): d = 136.7 (dd, 1JP,C = 25.7 Hz, JP,C
=
2
12.7 Hz, i-CPh),135.8 (dd, 2JP,C = 10.4 Hz, JP,C = 1.3 Hz, i-CMes),133.3
(br, o-CMes),133.3 (d, 5JP,C = 2.0 Hz, p-CMes),132.7 (dd, 3JP,C = 15.5 Hz,
4JP,C = 4.8 Hz, m-CPh),128.2 (br, m-CMes),126.4 (d, 4JP,C = 6.1 Hz, o-
3
CPh),125.6 (s, p-CPh),118.4 (dd, 2JP,C = 7.6 Hz, JP,C = 1.0 Hz,N-CH),
3
19.0 (d, JP,C = 1.0 Hz, p-CH3),18.4 ppm (br s, o-CH3); 31P{1H} NMR
6
(C6D6,303 K): d = 131.0 (d, 2JP,P = 259 Hz,PN 2), À28.8 ppm (d,
2JP,P =259 Hz,PPh ); MS (EI,70 eV,410 K): m/z (%): 508(0.1) [M]+,
[7] a) G. M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46,467;
b) G. M. Sheldrick,SHELXL-97,University of Göttingen, 1997.
[8] Average value Æ 3 standard deviations as result of a query in the
2
323(100) [PN2C20H24]+,185(17) [PPh 2]+; correct elemental analysis.
5b: m.p. 978C,yield 65%. 1H NMR (C6D6): d = 6.77 (s,4H, m-
CH),5.85 (d,2H, 3JP,H = 0.5 Hz,N-CH),2.45 (s,12H, o-CH3),2.34 (q,
À
À
CCSD data base for P P distances in diphosphanes R2P PR2
(R = nonmetal substituent).
4H, 3JH,H = 7.5 Hz,CH 2),2.12 (s,6H, p-CH3),1.73 (br dq,4H, JH,H
=
3
7.5 Hz, JP,H = 9.3 Hz,CH 2),1.07 (t,6H, 3JH,H = 7.5 Hz,CH 3),1.06 ppm
[9] S. L. Hinchley,C. A. Morrison,D. W. H. Rankin,C. L. B.
Macdonald,R. J. Wiacek,A. Voigt,A. H. Cowley,M. F. Lappert,
G. Gundersen,J. A. C. Clyburne,P. P. Power, J. Am. Chem. Soc.
2001, 123,9045.
(t,6H, 3JH,H = 7.5 Hz,CH 3); 13C{1H} NMR (C6D6): d = 152.2 (dd,
2JP,C = 8.9 Hz, 3JP,C = 2.6 Hz,PCC),143.4 (dd, 1JP,C = 22.4 Hz, JP,C
=
2
14.6 Hz,PC),136.9 (dd, 2JP,C = 7.4 Hz, 3JP,C = 1.7 Hz, i-C),136.1 (d,
5JP,C = 2.0 Hz, p-C),135.5 (dd, 3JP,C = 3.3 Hz, 4JP,C = 1.6 Hz, o-C),129.5
(d, 4JP,C = 1.1 Hz, m-C),120.9 (dd, 2JP,C = 8.8 Hz, 3JP,C = 1.2 Hz,N-CH),
21.0 (dd, JP,C = 22.5,0.9 Hz,CH 2),20.9 (d, JP,C = 1.6 Hz,CH 2),20.5 (d,
[10] H. R. G. Bender,E. Niecke,M. Nieger,H. Westermann,
Z.
Anorg. Allg. Chem. 1994, 620,1194.
[11] Average Æ 3 standard deviations as result of a query in the
6JP,C = 0.8 Hz, p-CH3),19.7 (dd, 4JP,C = 6.2 Hz, JP,C = 3.2 Hz, o-CH3),
5
À
À
CCSD data base for P C and C C distances in phospholes.
[12] All computations were carried out at the B3LYP/6-31g(d)-level
with the Gaussian program package: Gaussian 98 (Rev. A.7),
M. J. Frisch,G. W. Trucks,H. B. Schlegel,G. E. Scuseria,M. A.
Robb,J. R. Cheeseman,V. G. Zakrzewski,J. A. Montgomery,
R. E. Stratmann,J. C. Burant,S. Dapprich,J. M. Millam,A. D.
Daniels,K. N. Kudin,M. C. Strain,O. Farkas,J. Tomasi,V.
Barone,M. Cossi,R. Cammi,B. Mennucci,C. Pomelli,C.
Adamo,S. Clifford,J. Ochterski,G. A. Petersson,P. Y. Ayala,Q.
Cui,K. Morokuma,D. K. Malick,A. D. Rabuck,K. Raghava-
chari,J. B.Foresman,J. Cioslowski,J. V. Ortiz,B. B. Stefanov,G.
Liu,A. Liashenko,P. Piskorz,I. Komaromi,R. Gomperts,R. L.
Martin,D. J. Fox,T. Keith,M. A. Al-Laham,C. Y. Peng,A.
Nanayakkara,C. Gonzalez,M. Challacombe,P. M. W. Gill,B. G.
Johnson,W. Chen,M. W. Wong,J. L. Andres,M. Head-Gordon,
E. S. Replogle,J. A. Pople,Gaussian,Inc.,Pittsburgh PA, 1998.
[13] NBO 5.0: E. D. Glendening,J.K. Badenhoop,A. E. Reed,J. E.
Carpenter,J. A. Bohmann,C. M. Morales,F. Weinhold,Theo-
18.3 (dd, 3JP,C = 5.7 Hz, 4JP,C = 2.4 Hz,CH 3),16.6 ppm (d, 4JP,C
=
1.1 Hz,CH 3); 31P{1H} NMR (C6D6,303 K): d = 147.1 (d, JP,P
=
1
188 Hz,PN ),23.1 ppm (d, 1JP,P = 188 Hz,P phosphole); MS (EI,70 eV,
2
380 K): m/z (%): 518(0.1) [M]+,323(100) [PN 2C20H24]+,196(14)
[PC12H20]+; correct elemental analysis.
Received: March 15,2004
Keywords: addition reactions · bond polarization · insertions ·
.
phosphanes · phosphorus heterocycles
[1] G. A. Gallup , Valence Bond Methods—Theory and Applica-
tions,Cambridge University Press,Cambridge, 2002.
[2] D. Gudat,A. Haghverdi,M. Nieger, Angew. Chem. 2000, 112,
3211; Angew. Chem. Int. Ed. 2000, 39,3084.
Angew. Chem. Int. Ed. 2004, 43, 4801 –4804
ꢀ 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4803