Lithium, potassium, and tin(II) complexes of novel 3-(iminophosphorano)-1-phosphaallyl and 2-(iminophosphorano)-1-phosphaallyl ligands

Article abstract of DOI:10.1021/om020422c

Reaction of Ph₂P(C≡CBu^t)=NSiMe₃ (1) with KP(H)Ph afforded 3-(iminophosphorano)-1-phosphaallyl potassium, [K{P(Ph)C(Bu^t)=C(H)P(Ph)₂=NSiMe₃}(OEt₂ )₃] [3·(OEt₂)₃], which was recrystallized from Et₂O to give a solvent-free complex, [K{P(Ph)C(Bu_t)=C(H)P(Ph)₂=NSiMe₃}]_∞ (3). Treatment of Me₂P(C≡CPh)=NSiMe₃ (2) with LiP(R)Ph (R = H, SiMe₂Bu^t) formed 2-(iminophosphorano)-1-phosphaallyllithium, [Li{P(Ph)C{=C(R)Ph}P(Me)₂=NSiMe₃}-(THF)_n] (R = H, n = 1.5, 4; R = SiMe₂Bu^t, n = 2, 5), via a hydrogen or SiMe₂Bu^t group 1,3-P → C migration. Reaction of 4 or 5 with SnCl₂ in 2:1 ratio in Et₂O yielded P, N-chelating tin(II) complexes [Sn{P(Ph)C{=C(R)Ph}P(Me)₂=NSiMe₃}₂] (R = H, 6; R = SiMe₂Bu^t, 7). Complex 6 was also obtained by treatment of ClSnN(SiMe₃)₂ with 1 equiv of 4. X-ray data are provided for 3, 5, and 6. Complex 3 is polymeric in the solid state without coordinated solvent molecules, whereas both crystalline 5 and 6 are monomeric.

Full text of DOI:10.1021/om020422c

Organometallics 2002, 21, 4641-4647
4641
Lith iu m , P ota ssiu m , a n d Tin (II) Com p lexes of Novel
3-(Im in op h osp h or a n o)-1-p h osp h a a llyl a n d
2-(Im in op h osp h or a n o)-1-p h osp h a a llyl Liga n d s
Zhong-Xia Wang* and Ye-Xin Li
Department of Chemistry, University of Science and Technology of China,
Hefei, Anhui 230026, People’s Republic of China
Received May 28, 2002
Reaction of Ph2P(CtCBut)dNSiMe3 (1) with KP(H)Ph afforded 3-(iminophosphorano)-1-
phosphaallyl potassium, [K{P(Ph)C(But)dC(H)P(Ph)2dNSiMe3}(OEt2)3] [3‚(OEt2)3], which
was recrystallized from Et2O to give a solvent-free complex, [K{P(Ph)C(But)dC(H)P(Ph)2dN-
SiMe3}]∞ (3). Treatment of Me2P(CtCPh)dNSiMe3 (2) with LiP(R)Ph (R ) H, SiMe2But)
formed 2-(iminophosphorano)-1-phosphaallyllithium, [Li{P(Ph)C{dC(R)Ph}P(Me)2dNSiMe3}-
(THF)n] (R ) H, n ) 1.5, 4; R ) SiMe2But, n ) 2, 5), via a hydrogen or SiMe2But group 1,3-P
f C migration. Reaction of 4 or 5 with SnCl2 in 2:1 ratio in Et2O yielded P, N-chelating
tin(II) complexes [Sn{P(Ph)C{dC(R)Ph}P(Me)2dNSiMe3}2] (R ) H, 6; R ) SiMe2But, 7).
Complex 6 was also obtained by treatment of ClSnN(SiMe3)2 with 1 equiv of 4. X-ray data
are provided for 3, 5, and 6. Complex 3 is polymeric in the solid state without coordinated
solvent molecules, whereas both crystalline 5 and 6 are monomeric.
Ch a r t 1
In tr od u ction
Phosphoraniminato and iminophosphorane ligands,
especially functionalized iminophosphorane ligands,
have attracted intensive attention in recent years. The
nature of the highly polar P-N bond in the ligand
makes a compound of this kind versatile in both
coordinate and organometallic chemistry.1-3 Examples
include N, N-chelating ligands such as iminophospho-
amides (I in Chart 1),4 3-(iminophosphorano)-1-azaallyls
* Corresponding author. E-mail: zxwang@ustc.edu.cn.
(1) (a) Cristau, H. J .; Taillefer, M.; Rahier, N. J . Organomet. Chem.
2002, 646, 94. (b) Dehnicke, K.; Krieger, M.; Massa, W. Coord. Chem.
Rev. 1999, 182, 19. (c) Dehnicke, K.; Weller, F. Coord. Chem. Rev. 1997,
158, 103. (d) Witt, M.; Roesky, H. W. Chem. Rev. 1994, 94, 1163.
(2) (a) Aris, M. W.; Goosen, M.; Elsevier, C. J .; Veldman, N.;
Kooijman, H.; Spek, A. L. Inorg. Chim. Acta 1997, 264, 43. (b) Aris,
M. W.; Vrieze, K.; Ernsting, J . M.; Elsevier, C. J .; Veldman, N.; Spek,
A. L.; Katti, K. V.; Barnes, C. L. Organometallics 1996, 15, 2376. (c)
Katti, K. V.; Batchelor, R. J .; Einstein, F. W. B.; Cavell, R. G. Inorg.
Chem. 1990, 29, 810. (d) Katti, K. V.; Cavell, R. G. Inorg. Chem. 1989,
28, 3033.
(3) (a) Hascall, T.; Ruhlandt-Senge, K.; Power, P. P. Angew. Chem.,
Int. Ed. Engl. 1994, 33, 356. (b) Stephan, D. W. Can. J . Chem. 2002,
80, 125. (c) Courtenay, S.; Mutus, J . Y.; Schurko, R. W.; Stephan, D.
W. Angew. Chem., Int. Ed. 2002, 41, 498. (d) Stephan, D. W.; Stewart,
J . C.; Guerin, F.; Spence, R. E. V. H.; Xu, W.; Harrison, D. G.
Organometallics 1999, 18, 1116.
(II in Chart 1),5 and (iminophosphorano)methanides (III
in Chart 1),6 and C, N-chelating ligands such as imino-
phosphoranato with a variety of substituents (IV in
Chart 1).7 Bis(iminophosphorano)methanides (V in Chart
(5) (a) Hitchcock, P. B.; Lappert, M. F.; Wang, Z.-X. J . Chem. Soc.,
Dalton Trans. 1997, 1953. (b) Barluenga, J .; Lopez, F.; Palacios, F. J .
Chem. Res. 1985, (S) 211, (M) 2541.
(4) (a) Vollmerhaus, R.; Shao, P.; Taylor, N. J .; Collins, S. Organo-
metallics 1999, 18, 2731. (b) Muller, E.; Muller, J .; Olbrich, F.; Bruser,
W.; Knapp, W.; Abeln, D.; Edelmann, F. T. Eur. J . Inorg. Chem. 1998,
87. (c) Kilimann, U.; Noltemeyer, M.; Schafer, M.; Herbst-Irmer, R.;
Schmidt, H.-G.; Edelmann, F. T. J . Organomet. Chem. 1994, 469, C27.
(d) Dufour, N.; Caminade, A.-M.; Basso-Bert, M.; Igau, A.; Majoral,
J .-P. Organometallics 1992, 11, 1131. (e) Witt, M.; Roesky, H. W.;
Stalke, D.; Pauer, F.; Henkel, T.; Sheldrick, G. M. J . Chem. Soc., Dalton
Trans. 1989, 2173. (f) Witt, M.; Stalke, D.; Roesky, H. W.; Sheldrick,
G. M. J . Chem. Soc., Dalton Trans. 1991, 663. (g) Steiner, A.; Stalke,
D. Inorg. Chem. 1993, 32, 1977. (h) Recknagel, A.; Witt, M.; Edelmann,
F. T. J . Organomet. Chem. 1989, 371, C40. (i) Straub, B. F.; Eisen-
tra¨ger, F.; Hofmann, P. J . Chem. Soc., Chem. Commun. 1999, 2507.
(6) Leung, W.-P.; Wang, Z.-X.; Li, H.-W.; Yang, Q.-C.; Mak, T. C.
W. J . Am. Chem. Soc. 2001, 123, 8123.
(7) (a) Said, M.; Thornton-Pett, M.; Bochmann, M. Organometallics
2001, 20, 5629. (b) Said, M.; Thornton-Pett, M.; Bochmann, M. J . Chem.
Soc., Dalton Trans. 2001, 2844. (c) Hitchcock, P. B.; Lappert, M. F.;
Uiterweerd, P. G. H.; Wang, Z.-X. J . Chem. Soc., Dalton Trans. 1999,
3413. (d) Hitchcock, P. B.; Lappert, M. F.; Wang, Z.-X. J . Chem. Soc.,
Chem. Commun. 1997, 1113. (e) Mu¨ller, A.; Neumu¨ller, B.; Dehnicke,
K. Chem. Ber. 1996, 129, 253. (f) Mu¨ller, A.; Neumu¨ller, B.; Dehnicke,
K. Angew. Chem., Int. Ed. Engl. 1997, 36, 2350. (g) Mu¨ller, A.; Krieger,
M.; Neumu¨ller, B.; Dehnicke, K.; Magull, J . Z. Anorg. Allg. Chem. 1997,
623, 1081. (h) Lo´pez-Ortiz, F.; Pela´ez-Arango, E.; Tejerina, B.; Pe´rez-
Carren˜o, E.; Garc´ıa-Granda, S. J . Am. Chem. Soc. 1995, 117, 9972.
10.1021/om020422c CCC: $22.00 © 2002 American Chemical Society
Publication on Web 09/24/2002

4642 Organometallics, Vol. 21, No. 22, 2002
Wang and Li
Sch em e 1
1) can act as N, N- or C, N-chelating ligands depending
on the nature of the metal atom and other ligands on
the metal.8 These anions are excellent chelating agents
for a wide range of metals, including main group and
transition metals as well as lanthanides. Recently, new
dianionic ligands (VI)9 were reported and a series of
main group and transition metal complexes based on
these and related ligands have been obtained.6,10 Such
ligands showed versatile bonding modes and reactivity.
For example, complexes of group 4 metals and sa-
marium with such ligands reveal carbon-metal double-
bond character (VII in Chart 1),10a,11 while the com-
plexes of chromium,12 aluminum,13 and group 14
metals10b display bonding modes as shown in structure
VIII (Chart 1) or similar structures. We aimed to design
and synthesize new ligands that combine the advan-
tages of iminoposphoranes and phosphides: this class
of ligands possess a combination of hard and soft donor
(or bonding) atoms and have different features associ-
ated with each donor atom that provided unique reac-
tivity to their metal complexes.14 A number of neutral
P, N ligands have been known.15 However, anionic P,
N ligands are relatively rare.16 We report here the
synthesis and characterization of lithium, potassium,
and tin(II) derivatives of monoanionic P, N-centered 3-
or 2-(iminophosphorano)-1-phosphaallyl ligands.
R2P(Br)dNSiMe3 (R ) Ph, Me)17 with appropriate
alkynyllithium.18 Both 1 and 2 are colorless distillable
liquids. Their EI mass spectra showed respective mo-
lecular ions. The IR spectrum of each compound exhib-
ited carbon-carbon triple-bond absorption. The 1H,
13C{1H}, and 31P{1H} NMR spectral data were also con-
sistent with the presumed structures. Treatment of 1
with an equimolar amount of KP(H)Ph in THF resulted
in a deep red solution. Removal of THF and crystalliza-
tion from Et2O afforded a red crystalline potassium
complex, [K{P(Ph)C(But)dCHP(Ph)2dNSiMe3}(OEt2)3],
[3‚(OEt2)3], which was recrystallized slowly from Et2O
at room temperature to form solvent-free crystals of 3
(Scheme 1). It seems that the Et2O molecules in 3‚
(OEt2)3 are loosely bound in 3. LiP(H)Ph or NaP(H)Ph
reacted similarly with 1, but only oily products were
Resu lts a n d Discu ssion
The P-alkynyl iminophosphoranes R2P(CtCR1)d
NSiMe3 (R ) Ph, R1 ) But, 1; R ) Me, R1 ) Ph, 2) were
prepared in good yields by stoichiometric reaction of
1
obtained. The H NMR spectrum of each oily product
showed the presence of appropriate groups with impuri-
ties. No attempts were made to further purify them.
Formation of complex 3 is postulated to involve a
Michael-type addition of [P(H)Ph]- to iminophosphorane
1 followed by a 1,3-hydrogen shift from phosphorus to
carbon. The related examples include base-catalyzed
Michael addition of diphenylphosphane to diphenyl
vinyl iminophosphoranes19 and addition of primary
amines to 1-alkynyl phosphine oxides.20 Complex
3‚(OEt2)3 is soluble in Et2O and benzene, but solvent-
free crystalline 3 is only partly soluble in Et2O and
(8) (a) Gamer, M. T.; Roesky, P. W. J . Organomet. Chem. 2002, 647,
123. (b) Wei, P. R.; Stephan, D. W. Organometallics 2002, 21, 1308.
(c) Gamer, M. T.; Roesky, P. W. Z. Anorg. Allg. Chem. 2001, 627, 877.
(d) Babu, R. P. K.; Aparna, K.; McDonald, R.; Cavell, R. G. Organo-
metallics 2001, 20, 1451. (e) Gamer, M. T.; Dehnen, S.; Roesky, P. W.
Organometallics 2001, 20, 4230. (f) Al-Benna, S.; Sarsfield, M. J .;
Thornton-Pett, M.; Ormsby, D. L.; Maddox, P. J .; Bre`s, P.; Bochmann,
M. J . Chem. Soc., Dalton Trans. 2000, 4247. (g) Kasani, A.; McDonald,
R.; Cavell, R. G. Organometallics 1999, 18, 3775. (h) Ong, C. M.;
McKarns, P.; Stephan, D. W. Organometallics 1999, 18, 4197. (i)
Imhoff, P.; Gu¨lpen, J . H.; Vrieze, K.; Smeets, W. J . J .; Spek, A. L.;
Elsevier, C. J . Inorg. Chim. Acta 1995, 235, 77. (j) Aris, M. W.; Vrieze,
K.; Ernsting, J . M.; Elsevier, C. J .; Veldman, N.; Spek, A. L.; Katti, K.
V.; Barnes, C. L. Organometallics 1996, 15, 2376. (k) Imhoff, P.;
Vanasselt, R.; Ernsting, J . M.; Vrieze, K.; Elsevier, C. J .; Smeets, W.
J . J .; Spek, A. L.; Kentgens, A. P. M. Organometallics 1993, 12, 1523.
(9) (a) Kasani, A.; Babu, R. P. K.; McDonald, R.; Cavell, R. G. Angew.
Chem., Int. Ed. 1999, 38, 1483. (b) Ong, C. M.; Stephan, D. W. J . Am.
Chem. Soc. 1999, 121, 2939.
(10) (a) Cavell, R. G.; Babu, R. P. K.; Aparna, K. J . Organomet.
Chem. 2001, 617-618, 158. (b) Leung, W.-P.; Wang, Z.-X.; Li, H.-W.;
Mak, T. C. W. Angew. Chem., Int. Ed. 2001, 40, 2501.
(11) Aparna, K.; Babu, R. P. K.; McDonald, R.; Cavell, R. G. Angew.
Chem., Int. Ed. 2001, 40, 4400.
(12) Kasani, A.; McDonald, R.; Cavell, R. G. J . Chem. Soc., Chem.
Commun. 1999, 1993.
(13) Aparna, K.; McDonald, R.; Ferguson, M.; Cavell, R. G. Organo-
metallics 1999, 18, 4241.
1
slightly soluble in benzene. The H NMR spectrum of
3‚(OEt2)3 exhibited two sets of signals of the ligand with
the same intensity of corresponding signals, showing
that 3‚(OEt2)3 may be dimeric, and in the dimer the two
ligands adopt different coordination patterns. Interest-
ingly, after the solution was left standing for a week at
room temperature, the 1H and 13C{1H} NMR spectra
displayed only one set of signals of the ligand. The
31P{1H} NMR spectrum gave P(III) and P(V) signals at
4.48 and 19.64 ppm, respectively. This is attributed to
a slow change of the coordination modes on K in
solution.
(14) Kwong, F. Y.; Chan, A. S. C.; Chan, K. S. Tetrahedron 2000,
56, 8893.
Crystalline complex 3 is a polymer, revealed by single-
crystal X-ray diffraction (Figure 1). Figure 2 illustrates
how the structure propagates. Each potassium atom is
coordinated by the nitrogen atom and the P(III) atom
(15) (a) Crociani, B.; Antonaroli, S.; Bandoli, G. Organometallics
1999, 18, 1137. (b) Katti, K. V.; Cavell, R. G. Organometallics 1988, 7,
2236. (c) Katti, K. V.; Cavell, R. G. Organometallics 1989, 8, 2147. (d)
van den Beuken, E. K.; Meetsma, A.; Kooijman, H.; Spek, A. L.;
Feringa, B. L. Inorg. Chim. Acta 1997, 264, 171. (e) Katti, K. V.;
Santarsiero, B. D.; Pinkerton, A. A.; Cavell, R. G. Inorg. Chem. 1993,
32, 5919. (f) J ose´ Vicente, J .; Arcas, A.; Bautista, D.; Ram´ırez de
Arellano, M. C. Organometallics 1998, 17, 4544.
(16) See, for example: (a) Ahmad, M.; Perera, S. D.; Shaw, B. L.;
Thornton-Pett, M. Inorg. Chim. Acta 1996, 245, 59. (b) Paasch, K.;
Nieger, M.; Niecke, E. Angew. Chem., Int. Ed. Engl. 1995, 34, 2369.
(c) Westerhausen, M.; Digeser, M. H.; Schwarz, W. Inorg. Chem. 1997,
36, 521. (d) Ashby, M. T.; Li, Z. Inorg. Chem. 1992, 31, 1321.
(17) Wisian-Neilson, P.; Neilson, R. Inorg. Chem. 1980, 19, 1875.
(18) (a) Geissler, M.; Kopf, J .; Weiss, E.; Neugebauer, W.; Schleyer,
P. V. R. Angew. Chem., Int. Ed. Engl. 1987, 26, 587. (b) Eisch, J . J .
Organomet. Synth. 1981, 2, 130.
(19) Alajar´ın, M.; Lo´pez-Leonardo, C.; Llamas-Lorente, P. Tetra-
hedron Lett. 2001, 42, 605.
(20) Portnoy, N. A.; Morrow, C. J .; Chattha, M. S.; Williams, J . C.,
J r.; Aguiar, A. M. Tetrahedron Lett. 1971, 1397.

Lithium, Potassium, and Tin(II) Complexes
Organometallics, Vol. 21, No. 22, 2002 4643
F igu r e 1. ORTEP representation of [K{P(Ph)C(But)dC(H)P(Ph)2dNSiMe3}] with neighboring ligand. Selected bond lengths
(Å) and angles (deg): K(1)-N(1), 2.831(7); K(1)-C(26A), 3.378(11); K(1)-P(2), 3.265(4); K(1)-Si(1), 3.626(4); K(1)-C(15),
3.276(8); N(1)-P(1), 1.566(7); K(1)-P(2A), 3.278(3); P(1)-C(1), 1.760(8); K(1)-C(11A), 3.309(10); C(1)-C(2), 1.355(10);
P(2)-C(2), 1.800(8); N(1)-K(1)-P(2), 77.82(15); P(2)-K(1)-P(2A), 153.25(8); N(1)-K(1)-P(2A), 95.34(15); C(2)-P(2)-
K(1), 110.5(3); C(1)-P(1)-N(1), 119.2(4); C(1)-C(2)-P(2), 117.4(6); C(2)-C(1)-P(1),129.3(7).
F igu r e 2. Representation of crystalline complex 3, showing how the structure propagates.
from one ligand and by the P(III) atom from an adjacent
ligand in the polymeric chain. Thus, each P(III) atom
acts as a bridge between two potassium atoms and the
[P(Ph2)dNSiMe3] group chelates as a sidearm to a
potassium via its nitrogen coordination. There are also
interactions between K(1) and Si(1), and C(15) and
C(11A), respectively [K(1)‚‚‚Si(1) ) 3.626(4) Å, K(1)‚‚‚
C(15) ) 3.276(8) Å, K(1)‚‚‚C(11A) ) 3.309(10) Å], and
agostic interactions with the protons of the trimethyl-
silyl methyl groups on Si(1) and Si(1A), respectively
[K(1)‚‚‚H(27c) ) 3.017 Å, K(1)‚‚‚H(26Ac) ) 2.793 Å]. The
K(1), N(1), P(1), C(1), C(2), and P(2) atoms form a
twisted six-membered ring. The K(1)-N(1) distance of
2.831(7) Å is comparable to those found in [K{CH-
(Ph2PdNSiMe3)2}(THF)2] [2.798(2) and 2.731(2) Å,
respectively]8c and [{{N(SiMe3)C(Ph)CH}2C5H3N-2,6}-
{K(TMEDA}2] [2.667(4)-2.961(6) Å].21 The K(1)-P(2)
and K(1)-P(2A) distances of 3.265(4) and 3.278(3) Å,
respectively, are comparable to those in [KP(H)C
6H2
-
But -2,4,6]x, ranging from 3.181(2) to 3.357(2) Å.22 The
3
P(2)-C(2) distance of 1.800(8) Å is longer than that of
a delocalized system, for example, 1.757(6) Å in [Li-
(TME)3{2,4,6-But C6H2PC(Ph)C(H)Ph}] (A),23 but shorter
3
than a normal P-C single bond, as found in A [1.879(7)
Å].23 The 1.355(10) Å C(1)-C(2) distance is comparable
to the corresponding distance in A [1.366(6) Å].23 The
facts imply that the negative charge is partly delocalized
on the P(2)-C(1)-C(2) unit. The C(1), C(2), P(1), and
N(1) atoms are not coplanar, and the torsion angle
between the C(1)C(2)P(1) plane and the C(2)P(1)N(1)
plane is 67.6°. The P(1)-N(1) distance of 1.566(7) Å is
indicative of a P-N double bond.24
(22) Rabe, G. W.; Yap, G. P. A.; Rheingold, A. L. Inorg. Chem. 1997,
36, 1990.
(21) Leung, W.-P.; Cheng, H.; Hou, H. L.; Yang, Q.-C.; Mak, T. C.
W. Organometallics 2000, 19, 5431.
(23) Niecke, E.; Nieger, M.; Wenderoth, P. J . Am. Chem. Soc. 1993,
115, 6989.

4644 Organometallics, Vol. 21, No. 22, 2002
Wang and Li
trans to the [P(Me)2dNSiMe3] group. The But group on
Si(2) adopts a trans conformation to the phenyl group
on P(2), thus minimizing steric repulsions between the
groups. The Li(1)-N(1) distance of 2.037(15) Å is within
the normal range as observed for lithium amides26 and
lithium iminophosphorances.7d,f,27 The Li(1)-P(2) dis-
tance of 2.652(12) Å is longer than those found in
[{Li(THF)2}2{PhPCH2CH2PPh}] (av 2.56 Å),28 [{Li-
(TMEDA)}2C6H4(PPh)2-1,2] (av 2.58 Å),29 and [Li(THF)2-
{MePC6H4-2-CH(C6H4-2-CHNMe2)NMe2}]30 (av 2.52 Å),
but shorter than those of [Li{CH2P(C6H4-2-CH2NMe2)2}]4
(av 2.736 Å).31 The 1.835(7) Å P(2)-C(6) distance is
longer than the corresponding distance in 3 [1.800(8)
Å], but slightly shorter than a P-C single bond.23 The
1.340(8) Å C(6)-C(7) distance is close to a carbon-
carbon double bond.23 The findings reveal that delocal-
ization of charge on the P(1)-C(6)-C(7) unit is very
limited. It may be better to describe the P(1)-C(6)-C(7)
unit as a combination of a carbon-carbon double bond
and an anionic P center.
F igu r e 3. ORTEP representation of complex 5. Selected
bond lengths (Å) and angles (deg): Li(1)-N(1), 2.037(15);
Li(1)-P(2), 2.652(12); Li(2)-N(2), 2.022(13); Li(2)-P(4),
2.605(12); P(2)-C(6), 1.835(7); C(6)-C(7), 1.340(8); P(1)-
C(6), 1.835(7); P(1)-N(1), 1.567(5); N(1)-Li(1)-P(2), 94.9(5);
P(2)-C(6)-C(7),121.0(6); P(2)-C(6)-P(1), 111.5(4); P(1)-
N(1)-Li(1), 109.2(4); C(6)-P(2)-Li(1), 86.3(4); C(6)-P(1)-
N(1), 110.1(3).
The ligand transfer reaction was carried out by
reaction of 4 and 5, respectively, with SnCl2 in a 2:1
ratio in Et2O (eq 2). The homoleptic tin(II) complexes
In contrast to the reaction described in Scheme 1, the
reaction of 2 with LiP(R)Ph (R ) H, SiMe2But)25 gave
different results (eq 1). In the reaction, [P(R)Ph]-
with the P, N-chelating ligands, 6 and 7, were obtained
in relatively low yields. Both 6 and 7 are solvent-free
red crystals. Complex 6 is air sensitive, while 7 is
comparatively stable to the air in the solid state.
Crystalline 7 was exposed to the air for a week without
decomposition, but is air-sensitive in an ether solution.
attacks at the triple-bond carbon adjacent to P(V),
followed by a 1,3 shift of hydrogen or the SiMe2But
group from phosphorus to carbon. Compared with the
reaction shown in Scheme 1, this different addition
orientation is attributed to polar reversion of the
carbon-carbon triple bond in 2 because of changes of
substituted groups on the P(V) and the triple-bond
carbon. It seems that the steric factors are nonessential
in the reactions. The 31P{1H} NMR spectrum of each of
4 and 5 showed two sharp signals corresponding to
P(III) and P(V) atoms, respectively. The 1H and 13C{1H}
NMR spectra of each complex showed signals of ap-
propriate groups, consistent with the proposed struc-
tures. The structure of 5 was also established by single-
crystal X-ray diffraction. The complex is monomeric and
crystallizes with two molecules in the asymmetric unit
(Figure 3, only one molecule shown). The lithium atom
is in a distorted tetrahedral environment and is rounded
by N(1) and P(2) of the ligand and two THF molecules.
The Li(1), P(2), C(6), P(1), and N(1) atoms constitute a
five-membered metallacycle. The SiMe2But group is
1
The H and 13C{1H} NMR spectra of each of complexes
6 and 7 exhibited a set of signals, showing an equivalent
coordination mode of the two ligands. The NMR spectra
also showed that the two P-methyls in a ligand had
different chemical environments, consistent with their
respective chemical structure. The 31P{1H} NMR spec-
trum of each complex showed two signals, and the
upfield one displayed satellites by tin coupling.
Attempts to prepare heteroleptic tin(II) complexes
with the P, N ligands by reactions of 4 with an
equimolar portion of SnCl2 and ClSnN(SiMe3)2,32 re-
(26) See for instance: (a) Knizek, J .; Krossing, I.; No¨th, H.; Schwenk,
H.; Seifert, T. Chem. Ber. 1997, 130, 1053. (b) Henderson, K. W.;
Dorigo, A. E.; Liu, Q.-Y.; Williard, P. G. J . Am. Chem. Soc. 1997, 119,
11855. (c) Clegg, W.; Henderson, K. W.; Horsburgh, L.; Mackenzie, F.
M.; Mulvey, R. E. Chem. Eur. J . 1998, 4, 53.
(27) Steiner, A.; Stalke, D. Angew. Chem., Int. Ed. Engl. 1995, 34,
1752.
(28) Anderson, D. M.; Hithcock, P. B.; Lappert, M. F.; Moss, I. Inorg.
Chim. Acta 1988, 141, 157.
(29) Anderson, D. M.; Hithcock, P. B.; Lappert, M. F.; Leung, W.-
P.; Zora, J . A. J . Organomet. Chem. 1987, 333, C13.
(30) Izod, K.; O’Shaughnessy, P.; Clegg, W. Organometallics 2002,
21, 641.
(24) (a) Imhoff, P.; van Asselt, R.; Elsevier, C. J .; Vrieze, K.; Goubitz,
K.; van Malssen, K. F.; Stam, C. H. Phosphorus Sulfur 1990, 47, 401.
(b) Corbridge, D. E. C. Phosphorus; Elsevier: Amsterdam, 1985; p 38.
(25) Yoshifuji, M.; Toyota, K.; Shibayama, K.; Inamoto, N. Chem.
Lett. 1983, 1653.
(31) Izod, K.; O’Shaughnessy, P.; Clegg, W. Organometallics 2001,
20, 648.
(32) Harris, D. H.; Lappert, M. F. J . Chem. Soc., Chem. Commun.
1974, 895.

Lithium, Potassium, and Tin(II) Complexes
Organometallics, Vol. 21, No. 22, 2002 4645
while the steric factors are nonessential. In the lithium
and potassium complexes, the negative charge is partly
delocalized or almost localized on phosphorus through
comparison of their bond lengths and geometries with
those of delocalized anionic 1-phosphaallyl systems. The
2-(iminophosphorano)-1-phosphaallyl ligands are suit-
able for the preparation of tin(II) compounds. We are
actively investigating the action of the ligands in
transition metal chemistry.
Exp er im en ta l Section
Gen er a l P r oced u r es. All experiments were performed
under nitrogen using standard Schlenk and vacuum line
techniques. Solvents were distilled under nitrogen over sodium-
benzophenone (THF, Et2O, and n-hexane) or CaH2 (CH2Cl2)
and degassed prior to use. CDCl3 and C6D6 were purchased
from Acros Organics and degassed and stored over activated
molecular sieves (CDCl3) or Na/K alloy (C6D6). PhCtCH and
LiBun were purchased from Acros Organics and used as ob-
tained. R2P(Br)dNSiMe3 (R ) Me, Ph),17 PhP(SiMe2But)Li,25
ClSnN(SiMe3)2,32 and ButCtCH35 were prepared according to
the literature. NMR spectra were recorded on a Bruker av400
spectrometer at ambient temperature. The chemical shifts of
1H and 13C{1H} NMR spectra are referenced to internal solvent
resonances; the 31P{1H} NMR spectra are referenced to
external 85% H3PO4. Infrared spectra were recorded as neat
liquid films on a Bruker VECTOR-22 spectrometer. EI mass
spectra were measured with a Perkin-Elmer TURBOMASS
instrument. Elemental analyses were performed by the Ana-
lytical Laboratory of Shanghai Institute of Organic Chemistry.
Syn th esis of R2P (CtCR1)dNSiMe3 (R ) P h , R1 ) Bu t,
1; R ) Me, R1 ) P h , 2). A solution of LiBun (14.7 mL of a 2.5
M solution in hexane, 36.6 mmol) was added dropwise to a
stirred solution of ButCtCH (3.0 g, 36.6 mmol) in 30 mL of
Et2O at -70 °C. The mixture was stirred at room temperature
for 2 h and then added dropwise to a cooled (-70 °C) Et2O
solution of Ph2P(Br)dNSiMe3 prepared in situ from Ph2PN-
(SiMe3)2 (13.8 g, 40 mmol) and Br2 (6.4 g, 40 mmol).17 The
mixture was allowed to warm to room temperature and stirred
overnight. Solvent was removed in vacuo, and the residue was
extracted with n-hexane. The extract was concentrated and
then distilled at reduced pressure to afford a colorless oil of
compound 1 (8.5 g, 66.1%), bp 122-125 °C/0.03 mmHg. IR:
F igu r e 4. ORTEP representation of complex 6. Selected
bond lengths (Å) and angles (deg): Sn(1)-N(1), 2.532(18);
Sn(1)-N(2), 2.562(15); Sn(1)-P(2), 2.591(7); Sn(1)-P(4),
2.598(7); P(1)-N(1), 1.58(2); P(3)-N(2), 1.592(18); P(1)-
C(6), 1.82(3); P(2)-C(6), 1.81(3); C(6)-C(7), 1.31(3); N(1)-
Sn(1)-N(2),159.80(13); N(2)-Sn(1)-P(4), 78.4(4); N(1)-
Sn(1)-P(4), 87.7(5); N(1)-Sn(1)-P(2), 78.7(5); P(2)-Sn(1)-
P(4), 92.49(4); P(1)-N(1)-Sn(1), 115.5(10); P(2)-C(6)-P(1),
120.0(13); P(2)-C(6)-C(7), 124(2).
spectively, were unsuccessful. The reaction with the
former produced unidentified species, and with the
latter afforded complex 6 in 42.1% yield.
The structure of complex 6 was further confirmed by
single-crystal X-ray diffraction. The structure (Figure
4) reveals that the molecule is monomeric in the solid
state. The coordination number of the central Sn is four,
and the lone pair of electrons on tin occupies an
additional coordination site. The N(1)-Sn(1)-P(2) angle
is almost equal to that of N(2)-Sn(1)-P(4), 78.7(5)° and
78.4(4)°, respectively. The N(1)-Sn(1)-N(2) angle of
159.80(13)° is much wider than that of P(2)-Sn(1)-P(4)
[92.49(4)°]. The mean Sn-N distance of 2.547 Å is
comparable with the Sn-N(1) distance of 2.511(6) Å in
[Sn[{N(SiMe3)2PPh2}2].33 The Sn-P bond distance of
average 2.595 Å falls within the range reported for
bonds between the anionic P center and Sn(II) (2.60-
2.80 Å).34 In addition, the structure also shows that the
phenyl group on the C-C double bond is trans to the
[P(Me)2dNSiMe3] group on the other side of the C-C
double bond.
ν
CtC (cm-1) 2166. 1H NMR (400.1 MHz, CDCl3, 298 K): δ 0.07
(s, 9H, SiMe3), 1.35 (s, 9H, But), 7.39-7.45 (m, 6H, Ph), 7.80-
7.85 (m, 4H, Ph). 13C{1H} NMR (100.6 MHz, CDCl3, 298 K):
δ 4.51 (d, J ) 4.43 Hz), 28.78 (d, J ) 2.31 Hz), 30.43, 76.82 (d,
J ) 144.26 Hz), 114.00 (d, J ) 22.84 Hz), 128.83, 128.96,
131.38, 131.50, 131.53, 137.16, 138.39. 31P{1H} NMR (161.9
MHz, CDCl3, 298 K): δ -20.52. MS(EI): m/z 353 [M+]. Anal.
Calcd for C21H28NPSi: C, 71.35; H, 7.98; N, 3.96. Found: C,
71.08; H, 7.75; N, 4.07.
Com p ou n d 2 was prepared similarly. To a stirred solution
of PhCtCH (8.1 mL, 73.75 mmol) in 100 mL of Et2O was added
dropwise a solution of LiBun (29.5 mL of a 2.5 M solution in
hexane, 73.75 mmol) at -60 °C. The reaction mixture was
stirred at room temperature for 2 h and then was added
dropwise to a stirred solution of Me2P(Br)dNSiMe3 (16.8 g,
73.68 mmol) in 100 mL of Et2O at -80 °C. The mixture was
stirred overnight at room temperature, and the solvent was
removed in vacuo. The residue was extracted with hexane, and
then successive concentration and distillation of the extract
at reduced pressure yielded a colorless oil identified as 2 (15.47
Con clu sion s
We have described the nucleophilic addition of
[P(R)Ph]- (R ) H or SiMe2But) to a P-alkynyl imino-
phosphorane, and through the reaction novel anionic P,
N ligands have been synthesized. Electronic effects of
the substituted groups on the carbon-carbon triple bond
and on the P(V) determine the addition orientations,
1
g, 84.3%), bp 90-93 °C/0.1 mmHg. IR: νCtC (cm-1) 2174. H
(33) Kilimann, U.; Noltemeyer, M.; Edelmann, F. T. J . Organomet.
Chem. 1993, 443, 35.
(34) (a) Mosqnera, M. E. G.; Hopkins, A. D.; Raithby, P. R.; Steiner,
A.; Rothenberger, A.; Words, A. D.; Wright, D. S. J . Chem. Soc., Chem.
Commun. 2001, 327, and references therein. (b) Bond, A. D.; Rothen-
berger, A.; Word, A. D.; Wright, D. S. J . Chem. Soc., Chem. Commun.
2001, 525.
NMR (400.1 MHz, C6D6, 298 K): δ 0.42 (s, 9H, SiMe3), 1.30
(d, J ) 14.07 Hz, 6H, PMe), 6.88-6.95 (m, 3H, Ph), 7.34-7.39
(35) (a) Kocienski, P. J . J . Org. Chem. 1974, 39, 3285. (b) Bartlett,
P. D.; Rosen, L. J . J . Am. Chem. Soc. 1942, 64, 543.

4646 Organometallics, Vol. 21, No. 22, 2002
Wang and Li
(m, 2H, Ph). 13C{1H} NMR (100.6 MHz, C6D6, 298 K): δ 2.52,
18.56 (d, J ) 88.53 Hz), 20.66 (d, J ) 85.70 Hz), 78.50, 84.34,
123.29, 129.0, 129.26, 132.82. 31P{1H} NMR (161.9 MHz, C6D6,
n-hexane. Concentration of the extract afforded purple crystals
of complex 5 (0.73 g, 51.1%), mp 142-144 °C. H NMR (400.1
1
MHz, C6D6, 298 K): δ 0.06 (s, 9H, SiMe3), 0.14-0.50 (b, 3H,
SiMe), 0.82-1.14 (b, 3H, SiMe), 1.29 (s, 9H, But), 1.42-1.46
(m, 8H, THF), 3.61-3.64 (m, 8H, THF), 6.83 (t, J ) 7.21 Hz,
1H, Ph), 7.03-7.07 (m, 1H, Ph), 7.11-7.18 (m, 6H, Ph), 7.38
(t, J ) 6.87 Hz, 2H, Ph). 13C{1H} NMR (100.6 MHz, C6D6, 298
K): δ 0.85, 4.86, 20.29, 26.05, 30.76, 68.97, 158.26 (dd, J )
63.38, 58.95 Hz), 166.27 (dd, J ) 30.58, 8.35 Hz), 19.75, 126.39,
127.99 (d, J ) 4.23 Hz), 129.18 (d, J ) 8.81 Hz), 129.43, 148.26
(t, J ) 11.67 Hz), 159.03, 159.62. 31P{1H} NMR (161.9 MHz,
C6D6, 298 K): δ -27.72, 17.74. Anal. Calcd for C25H40NP2-
SiLi: C, 62.60; H, 8.41; N, 2.92. Found: C, 62.89; H, 8.27; N,
3.69.
298 K): δ 38.97. MS (EI): m/z 249 [M+]. Anal. Calcd for C13H20
-
NPSi: C, 62.62; H, 8.08; N, 5.62. Found: C, 62.78; H, 7.85; N,
5.51.
Syn t h esis of [K{P (P h )C(Bu t )C(H )P (P h )2dNSiMe3}-
(OEt2)3] [3‚(OEt2)3]. To a suspension of potassium (0.08 g,
2.05 mmol) in 20 mL of THF was added PhPH2 (0.21 g, 1.91
mmol) at room temperature. After the potassium disappeared,
the resulting solution was added dropwise to a stirred solution
of Ph2P(CtCBut)dNSiMe3 (0.67 g, 1.91 mmol) in 10 mL of
THF at -80 °C. The reaction mixture was stirred at room
temperature for 6 h. Volatiles were removed at reduced
pressure, and the residual solid was washed with n-hexane.
The solid was dissolved in Et2O and then filtered. Concentra-
tion of the filtrate in vacuo afforded deep red crystals of
Syn th esis of [Sn {P (P h )C{dC(H)P h }P (Me)2dNSiMe3}2]
(6). SnCl2 (0.30 g, 1.58 mmol) was added to a stirred solution
of 4 (1.67 g, 3.25 mmol) in 30 mL of Et2O at -80 °C. The
mixture was warmed to room temperature and stirred over-
night. Volatiles were removed in vacuo, and the residue was
extracted with CH2Cl2. Concentration of the extract in vacuo
yielded red crystals of complex 6 (0.60 g, 45.0%), mp 274.5-
1
3‚(OEt2)3 (0.58 g, 41.9%), mp >300 °C. H NMR (400.1 MHz,
C6D6, 298 K): 0.21 (s, 9H, SiMe3), 0.26 (s, 9H, SiMe3), 1.07 (s,
9H, But), 1.09 (t, J ) 7.09 Hz, 36H, Et2O), 1.57 (s, 9H, But),
3.24 (q, J ) 7.09 Hz, 24H, Et2O), 5.67-5.77 (m, 2H, CH), 6.72-
6.78 (m, 1H, Ph), 6.81-6.98 (m, 10H, Ph), 7.21-7.34 (m, 5H,
Ph), 7.43-7.54 (m, 6H, Ph), 7.63-7.72 (m, 3H, Ph), 7.68-7.85
(m, 5H, Ph). After one week the NMR spectra of the sample
1
275.5 °C. H NMR (400.1 MHz, C6D6, 298 K): δ 0.26 (s, 18H,
SiMe3), 0.94 (d, J ) 12.19 Hz, 6H, PMe), 6.72 (dd, J ) 18.76,
25.30 Hz, 2H, CH), 6.91-6.97 (m, 4H, Ph), 7.05-7.13 (m, 8H,
Ph), 7.82-7.85 (m, 4H, Ph), 7,96 (d, J ) 7.25 Hz, 4H, Ph).
13C{1H} NMR (100.6 MHz, C6D6, 298 K): δ 5.41, 20.97 (dd, J
) 59.45, 11.97 Hz), 24.68 (d, J ) 52.51 Hz), 126.17, 129.00,
129.10, 132.28 (d, J ) 10.56 Hz), 133.26 (d, J ) 12.78 Hz),
138.48(d, J ) 22.03 Hz), 140.37 (d, J ) 33.30 Hz), 145.50 (dd,
J ) 59.66, 81.99 Hz), 147.30 (t, J ) 17.30 Hz). 31P{1H} NMR
(161.9 MHz, C6D6, 298 K): δ -42.28 with satellites (J )
1077.59 Hz), 31.09. Anal. Calcd for C38H52N2P4Si2Sn: C, 54.62;
H, 6.27; N, 3.35. Found: C, 54.63; H, 6.23; N, 3.38.
1
exhibited only one set of signals. H NMR (400.1 MHz, C6D6,
298 K): 0.19 (s, 9H, SiMe3), 1.11 (t, J ) 6.94 Hz, 18H, Et2O),
1.57 (s, 9H, But), 3.25 (q, J ) 6.94 Hz, 12H, Et2O), 5.83 (t, J )
27.48 Hz, 1H, CH), 6.97-7.13 (m, 11H, Ph), 7.87-7.90 (m, 4H,
Ph). 13C{1H} NMR (100.6 MHz, C6D6, 298 K): δ 5.11, 31.59
(d, J ) 8.8 Hz), 34.05, 122.91, 129.93, 130.39, 130.81, 131.74
(d, J ) 8.95 Hz), 132.06 (dd, J ) 126.14, 19.02 Hz), 133.71 (d,
J ) 16.20 Hz), 135.87 (d, J ) 21.60 Hz), 140.88, 141.87, 155.38.
31P{1H} NMR (161.9 MHz, C6D6, 298 K): δ 4.48, 19.64.
Recrystallization of 3‚(OEt2)3 from Et2O at room temperature
Syn th esis of [Sn {P (P h )C{dC(P h )SiMe2Bu t}P (Me)2dN-
SiMe3}2] (7). SnCl2 (0.26 g, 1.37 mmol) was added to a stirred
solution of complex 5 (1.63 g, 2.62 mmol) in 30 mL of Et2O at
-80 °C. The mixture was allowed to reach room temperature
and stirred overnight. Volatiles were removed in vacuo, and
the residue was extracted with CH2Cl2. The volume of the
extract was reduced to about 3 mL, and then 3 mL of Et2O
was added. The solution was stored overnight at 0 °C to afford
gave [K{P(Ph)C(But)C(H)P(Ph)2dNSiMe3}]∞ identified crys-
tallographically.
Syn th esis of [Li{P (P h )C{dC(H)P h }P (Me)2dNSiMe3}-
(THF )1.5] (4). A solution of LiBun (1.74 mL of a 2.5 M solution
in hexane, 4.35 mmol) was added dropwise to a stirred solution
of PhPH2 (0.48 g, 4.36 mmol) in 15 mL of THF at 0 °C. The
mixture was stirred at room temperature for 2 h and then
added dropwise to a solution of Me2P(CtCPh)dNSiMe3 (1.1
g, 4.42 mmol) in 10 mL of THF at -80 °C. The mixture was
stirred at room temperature for 6 h. Volatiles were removed
in vacuo. The residue was dissolved in Et2O and filtered.
Concentration of the filtrate gave purple crystals of complex
4 (1.07 g, 51.2%), mp 120 °C (dec). 1H NMR (400.1 MHz, C6D6,
298 K): δ 0.23 (s, 9H, SiMe3), 1.44 (d, J ) 11.68 Hz, 6H, PMe),
1.23-1.26 (m, 6H, THF), 3.44-3.47 (m, 6H, THF), 6.74-6.80
(m, 1H, dCH), 6.92-7.02 (m, 4H, Ph), 7.13-7.17 (m, 2H, Ph),
7.32-7.36 (t, J ) 7.32 Hz, 2H, Ph), 7.93 (d, J ) 7.96 Hz, 2H,
Ph). 13C{1H} NMR (100.6 MHz, C6D6, 298 K): δ 4.91, 19.81
(d, J ) 59.58 Hz), 25.88, 68.83, 121.32, 126.61, 127.72 (d, J )
7.04 Hz), 129.15, 130.25 (d, J ) 18.91 Hz), 131.00 (d, J ) 2.31
Hz), 131.51, 134.70 (d, J ) 17.20 Hz), 137.25 (d, J ) 23.23
Hz), 139.63 (d, J ) 24.75 Hz). 31P{1H} NMR (161.9 MHz, C6D6,
298 K): δ -46.60, 25.76. Anal. Calcd for C19H26NP2SiLi (THF
escaped from the complex): C, 62.46; H, 7.17; N, 3.83. Found:
C, 62.11; H, 7.55; N, 3.51.
1
red crystals of complex 7 (0.38 g, 26.0%), mp 282-284 °C. H
NMR (400.1 MHz, C6D6, 298 K): δ 0.16 (s, 18H, SiMe3), 0.25
(s, 6H, SiMe), 0.63 (s, 6H, SiMe), 1.04 (s, 18H, SiMe), 1.11 (d,
J ) 14.04 Hz, 6H, PMe), 1.53 (d, J ) 12.68 Hz, 6H, PMe),
6.97-7.06 (m, 10H, Ph), 7.27 (t, J ) 7.2 Hz, 4H, Ph), 7.34 (t,
J ) 7.6 Hz, 2H, Ph), 7.65-7.68 (m, 4H, Ph). 13C{1H} NMR
(100.6 MHz, C6D6, 298 K): δ 1.28, 2.55, 6.16, 20.44, 29.84,
24.31 (d, J ) 48.36 Hz), 25.84 (d, J ) 6.80 Hz), 124.96, 127.26,
129.61(d, J ) 4.93 Hz), 131.11(d, J ) 14.69 Hz), 145.36 (t, J
) 27.87 Hz), 149.67 (m), 156.89 (m). 31P{1H} NMR (161.9 MHz,
C6D6, 298 K): δ -26.02 with satellites (J ) 1031.26 Hz), 24.92.
Anal. Calcd for C50H80N2P4Si4Sn: C, 56.37; H, 7.58; N, 2.63.
Found: C, 56.22; H, 7.46; N, 2.61.
Rea ction of [Li{P (P h )C{dC(H)P h }P (Me)2dNSiMe3}-
(THF )1.5] w ith ClSn N(SiMe3)2. A solution of complex 4 (0.86
g, 1.82 mmol) in 20 mL of Et2O was added to a stirred solution
of ClSnN(SiMe3)2 (0.57 g, 1.81 mmol) in 20 mL of Et2O at -80
°C. The reaction mixture was allowed to warm to room
temperature and stirred overnight. Volatiles were removed in
vacuo, and the residue was extracted with CH2Cl2. Crystal-
lization from CH2Cl2 gave red crystals identified as 6 (0.32 g,
42.1% based on 4).
Cr ysta l Str u ctu r e Solu tion a n d Refin em en t for Com -
p lexes 3, 5, a n d 6. Crystals were mounted in Lindemann
Capillaries under nitrogen. Diffraction data were collected on
a Siemens CCD area-detector at 298(2) K (for 3) and 299(2) K
(for 5 and 6, respectively) with graphite-monochromated Mo
KR radiation (λ ) 0.71073 Å). A semiempirical absorption
Syn th esis of [Li{P (P h )C{dC(P h )SiMe2Bu t}P (Me)2dN-
SiMe3}(THF )2] (5). A solution of LiBun (0.89 mL of a 2.5 M
solution in hexane, 2.23 mmol) was added dropwise to a stirred
solution of PhP(H)SiMe2But (0.5 g, 2.23 mmol) in 15 mL of
THF at room temperature. The mixture was stirred for 2 h
and then added dropwise to a solution of Me2P(CtCPh)d
NSiMe3 (0.57 g, 2.29 mmol) in 10 mL of THF at -80 °C. The
mixture was stirred at room temperature for 6 h. Volatiles
were removed in vacuo, and the residue was extracted with

Lithium, Potassium, and Tin(II) Complexes
Organometallics, Vol. 21, No. 22, 2002 4647
Ta ble 1. Deta ils of th e X-r a y Str u ctu r e Deter m in a tion s of Com p lexes 3, 5, a n d 6
3
5
6
empirical formula
fw
C
27H34KNP2Si
C66H112Li2N2O4P4Si4
1247.70
C
38H52N2P4Si2Sn
501.68
835.57
cryst syst
space group
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
monoclinic
P2(1)/n
13.655(11)
10.678(8)
21.348(17)
90
100.412(15)
90
3061(4)
triclinic
P1h
monoclinic
Cc
19.605(4)
11.840(2)
18.611(4)
90
96.580(3)
90
4291.4(15)
4
1.293
1728
0.828
2.01 to 24.78
10 545
10.655(3)
17.776(5)
21.218(6)
103.262(6)
97.354(6)
94.270(5)
3857(2)
Z
4
4
Dcalcd (g/cm3)
F(000)
1.089
1064
0.331
1.94 to 23.34
12 860
2.149
2704
0.403
1.94 to 23.37
13 982
µ (mm-1
)
θ range for data collecn (deg)
no. of reflns collected
no. of indep reflns (Rint
)
4316 (Rint ) 0.1654)
4316/1/293
0.794
R1 ) 0.0637
wR2 ) 0.1395
R1 ) 0.2344
wR2 ) 0.1915
0.665 and -0.294
10463 (Rint ) 0.0895)
10 463/0/739
0.644
R1 ) 0.0556
wR2 ) 0.0653
R1 ) 0.2863
wR2 ) 0.1081
0.191 and -0.170
6513 (Rint ) 0.0410)
6513/2/436
0.877
R1 ) 0.0420
wR2 ) 0.0584
R1 ) 0.0873
wR2 ) 0.0698
0.299 and -0.463
no. of data/restraints/params
goodness of fit on F2
final R indicesa [I > 2σ(I)]
R indices (all data)
largest diff peak and hole (e‚Å-3
)
R1 ) {∑||Fo| - |Fc||}/{∑|Fo|}; wR2 ) [{∑w(Fo - Fc2)2}/{∑w(Fo4)}]1/2
.
a
2
correction was applied to the data. The structures were solved
by direct methods (SHELXS-97)36 and refined against F2 by
full-matrix least-squares using SHELXL-97.37 Hydrogen atoms
were placed in calculated positions. The anomalous thermal
parameters on C(18) and C(35) in Figure 4 infer some disorder,
but attempts to model the disorder were unsatisfactory.
Crystal data and experimental details of the structure deter-
minations are listed in Table 1.
Ack n ow led gm en t. We are grateful for financial
support of this work from NSFC (Grant No. 20072035).
We wish to acknowledge Professors D.-Q. Wang and J .-
M. Dou for determining the crystal structures.
Su p p or tin g In for m a tion Ava ila ble: Details of the X-ray
structure determinations of 3, 5, and 6. Crystallographic files
in CIF format for the structure determinations of 3, 5, and 6.
This material is available free of charge via the Internet at
http://pubs.acs.org.
(36) Sheldrick, G. M. Acta Crystallogr., Sect. A 1990, 46, 467.
(37) Sheldrick, G. M. SHELXL97, Programs for structure refine-
ment; Universita¨t Go¨ttingen, 1997.
OM020422C