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Magnesium PhosphidesЦSynthesis and Structure of [Mg(PHPh)2(tmeda)].

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the solvent gave a usually oily residue, which was dissolved in ca. 50 m L of
ethyl acetate. Addition of hexane until the solution became cloudy resulted
i n the crystallization of the compounds 7 at -20°C (cf. Table I).
B) Synthesis of 22: 20 (30 mmol) was added to a solution of 5 (30 mmol)
in benzene prepared according to A above, and the reaction mixture was
heated at reflux for 2 h. After cooling to room temperature, the reaction mixture was worked u p as described under A (cf. Table 2).
Received: July 21, 1986;
revised: October 6, 1986 [ Z 1864 IE]
German version: Angew. Chem. 99 (1987) 64
[I] H. J. Bestmann, A. J. Kos, K. Witzgall, P. von R. Schleyer, Chem. Ber.
119(1986) 1331.
[2] A. M. van Leusen, B. A. Reith, A. J. W. ledema, J. Strating, Recl. Trau.
Chim. Puy.r-Bus 91 (1972) 37.
[3] C. Brouquet, M. Simalty, Tetrahedron Lett. 1972, 933; C. Broquet, Tetruhedrrm 29 (1973) 3595.
141 H. J. Bestmann, R. Besold, D. Sandmeier, Tetrahedron Lett. 1975. 2293:
H. J. Bestmann, D. Sandmeier, Angew. Chem. 87 (1975) 630; Angew.
Chem. i n t . Ed. Engl. 14 (1975) 634; Chem. Ber. 113 (1980) 274.
15) E. J. Corey, J . Kang, J . Am. Chem. Soc. 104 (1982) 4724; cf., however, B.
Schaub, T. Jenny, M. Schlosser, Tetrahedron Lett. 25 (1984) 4097; E. J.
Corey, J. Kang, K. Kyler, ibid. 26 (1985) 555; B. Schaub, M. Schlosser,
rbrd 26 (1985) 1623.
161 H. J. Bestmann, S . Pfohl, Justus Liebigs Ann. Chem. 1974. 1688.
171 H. J. Bestmann, G. Schmid, Chem. Ber. 113 (1980) 3369.
[8] T. A. Albright, P. Hofmann, A. R. Rossi, Nulurforsch. B 35 (1980) 343.
[9] Correct elemental analyses and spectroscopic data were obtained for all
new compounds.
[lo] A. J. Speziale, K. W. Ratts, J . Am. Chem. Soc. 85 (1963) 2790.
[ I l l Synthesis of 6g: cf. H. Frauenrath, T. Philipps, Tetrahedron 42 (1986)
1135. We thank Dr. Fruuenrurh for a large amount of 6g.
[I21 S. T. D. Cough, S . Trippett, J . Chem. SOC.1962, 2333.
metalate PH2Ph in heptane under mild conditions. The
product, 1, is assumed to have a polymeric structure containing bridging PHPh' groups which are cleaved by tetramethylethylenediamine (TMEDA) to yield a monomeric
hydrocarbon-soluble bis(phosphid0) complex, 2.
Compounds 1 and 2 show characteristic v(P-H) absorptions at 2280 and 2262/2250 c m - ' , respectively. The "PN M R spectrum of 2 shows two virtual triplets centered at
6 = - 123.65 and - 123.70 ppm in a ratio of ca. 2 : 1
( ( ' J + 3J)/2= 198.5 Hz, both triplets), corresponding presumably to coupling to two protons in each of the meso
and rac diastereoisomers that are possible for two chiral P
centers attached to magnesium. No 2sMg-3'P coupling was
evident and we were unable to obtain a "Mg-NMR spectrum,"] probably because of the low site symmetry at the
quadrupolar 2sMg nuclei.
Magnesium Phosphides-Synthesis and
Structure of IMg(PHPh),(tmeda)l**
By Evamarie Hey, Lutz M . Engelhardt. Colin L . Raston,*
and Allan H . White
The synthesis of organomagnesium reagents and their
utility in organic and organometallic chemistry is well
Inorganic magnesium reagents, however, remain
largely unexplored. For example, little is known about
magnesium p h ~ s p h i d e s ' ~and
. ~ ] their use as transfer agents
of PR? has not been investigated. We now report the synthesis and spectroscopic properties of the magnesium
phosphides lI3.,] and 2 F 1 and the X-ray crystal structure
determination of 2, which to our knowledge represents the
first crystallographic study of a magnesium phosphido
complex.
The relatively new reagent nBusBuMg, whose potential
is slowly being realized,"] was found to selectively mono2 PH2Ph
+
nEusBuMg
d [Mg(PHPh)2],
- C,",o
1
A
Me2N
1
+
TMEDA
+
\ I /
.' .Mg \HP
HP
Ph
[*I Dr. C. L. Raston, Dr. E. Hey, Dr.
[**I
NMe2
2
Ph
L. M. Engelhardt, Dr. A. H. White
Department of Physical and Inorganic Chemistry,
University of Western Australia
Nedlands 6009 (Australia)
We thank the Verband der Chemischen lndustrie fur a habilitation grant
for E. H . and the Deutsche Forschungsgemeinschaft and the Australian
Research Grants Scheme for supporting this work.
Angew Chem int. Ed. Engl. 26 11987) No. I
Fig. I . Crystal structure of 2 showing 20% thermal ellipsoids. Hydrogen
HI and H2 were located in a difference
atoms have arbitrary radii of 0.1
and bond angles [o]:Mg-P1,
m a p but not refined. Selected bond lengths
Mg-PZ 2.592(5), 2.587(5); Mg-NI, Mg-N2 2.306(8), 2.22668): PI-CI I 1.822(8),
P2-C21 1.821(10); PI-Mg-P2 122.5(1), PI-Mg-NI, PI-Mg-N2 100.9(3),
126.0(3), P2-Mg-NI. P2-Mg-N2 100.1(3), IlO.l(3), NI-Mg-N2 79.9(3),
Mg-PI-CI 1 122.6(4), Mg-P2-C2I 98.4(5).
A;
[A]
The X-ray structure of 2 (Fig.
obtained from a crystal selected from a bulk sample of inseparable isomers, was
of the ruc isomer. The magnesium centers have a distorted
tetrahedral environment with the P1 -Mg-P2 angle
(12241)") greater than the NI-Mg-N2 angle (79.9(3)").
The Mg-.P distances are virtually equivalent (2.592(5) and
2.587(5)A) and compare with those in MgP, (2.6082.862 A);"' the P-C distances are also equivalent. However, the Mg-P-C angles differ considerably (122.6(4) and
98.4(5) "). The associated hydrogen atom positions, although not satisfactorily resolved beyond difference map
artifacts, suggest pyramidal dispositions. Interestingly, the
nitrogen centers of monodentate amido ligands bound to
magnesium are trigonal.[']
The only other X-ray structures of phenylphosphido
complexes, namely, 3['"]and 4,l'll and the results of other
investigations"21 show that the properties and reactivity of
the PHPh" group are largely dependent on the nature of
the metal and coligands.
0 VCH Veriugsgeselischafi mbH. 0-6940 Weinheim. 1987
0570-0833/87/0101-0081$ 02.50/0
81
(OS(CO)~CI(
PHPh)( PPhJ2]
[W(=CCMe3)Cl2(PHPh)(PEt,),]
3
4
As&N,,-A
Diaminosulfane Derivative with Two
Bicyclic Arsino Sulfur Diimides""
The synthetic utility of magnesium phosphido reagents
in gaining access to other metal phosphido complexes is
being investigated. Interestingly, reaction of 5 with 1 gave
the known diphosphene complex 6"" rather than the expected phosphido
[NiCl2I(PR2CH2)d+ IMg(PHPh)21
5
-
1
[Ni(q-Ph- P= P-Ph)(( PR,CH,)&
6
Received: July 28, 1986;
revised: November 3, 1986 [Z 1879 IE]
German version: Angew. Chem. 99 (1987) 61
By Max Herberhold,* Karlheinz Guldner, Arfred Gieren,
Catalina Ruiz-PPrez. and Thomas Hiibner
The reaction of the salt K2SNz with organoarsenic chlorides has proved useful for the synthesis of the arsenicsubstituted sulfur diimides 1 and 2.".21According to the
X-ray structure analysis of 1 ( R = Ph), the sulfur diimide
skeleton in the bis(diorganoarsin0) sulfur diimides 1 has
the Z / Z
the eight-membered ring in 2
(R=tBu) has the boat form.[*] Compounds of type 1 were
first described in 1984;1'1eight-membered ring compounds
of type 2 with R=Me,l3l Ph,I4] and MesL4Ihad been obtained previously.
KS
, N,
+2
R2AsCL
CH3CN
- 2
KCI
>
R,i
R,As
/+
N
I ,R
ASlR
1
R = Me, tBu, cyclo-C6H,,. Ph
[I1
W. E. Lindsell in G. Wilkinson, F. G. A. Stone, E. W. Abel (Eds.): Comprehensive Organometallic Chemrsfry, Vol. I . Pergamon Press, Oxford
1982, p. 155; M. S. Vharasch, 0. Reinmuth: Grignard Reactions ofNonmerallic Substances. Constable, London 1954.
[2] A. Job, G. Dussolier, C. R. Hebd. Seances Acad. Sci. 184 (1927) 1454;
Chem. Absfr. 21 (1927) 3049; F. G. Mann, 1. T. Millar, J. Chem. SOC.
1952, 3039; K . Issleib, C. Rock Stuoh, 1. Duchek, E. Fluck, Z. Anorg.
Allg. Chem. 360 (1968) 77.
[3] K. Issleib, H. J . Deylig, Chem. Ber. 97 (1964) 946.
[4] Experimental procedure for 1 (exclusion of air and water): To PhPHI
(3.03 g, 27.5 mmol) in pentane (30 mL) was added a 0.7 M solution of
nBusBuMg in heptane (88 mL, 61.6 mmol). In an exothermic reaction a
white precipitate formed. The solution was then stirred at 25°C for 2 h.
The product (6.34 g, 95%) was collected, washed with pentane, and dried
in vacuo. I is pyrophoric, insoluble in pentane, hexane, and toluene,
and soluble in donor solvents. 1R: v(P-H)=2280 (w). v(Mg-P)=510300 cm - ' (br, structured).
[ 5 ] Experimental Procedure for 2 : 1 (2.03 g, 8.37 mmol) was dissolved in
TMEDA (4 mL). The resulting pale yellow solution was stirred for I h at
25"C, then pumped dry. The product was recrystallized from toluene/
pentane. Yield: 2.33 g (78%); white crystals, m.p.= IIS-12O"C (dec.).
'H-NMR (C6D,, 25% TMS): 6=7.66-6.97 (m, Ph), 5.05, 2.57 (d, J ( ' H "P)= 198.6 Hz, P-H), 1.94 (s, CH,), 1.86 ( s , CHZ). "P-NMR (CaD,,
2 5 T , 85% H3P04): 6 ( ' H decoupled)= - 123.64 (s), 6 ( ' H coupled)= - 123.65 (I), - 123.70 (1. J("P-'H)= 198.5 Hz). IR: v(P-H)=
2262 (m), 2250 (m) cm - I _
[6] J. J. Eisch, R. Sanchez, J. Organomet. Chem. 296 (1985) C 2 7 ; A. W.
Duff, P. B. Hutchcock, M. F. Lappert, R. G. Taylor, ibid. 293 (1985) 271 ;
M. Henderson, R. 1. Papasergio, C. L. Raston, A. H. White, M. F. Lappert, J. Chem. SOC.Chem. Commun. 1986, 672.
171 R. Benn, H. Lehmkuhl, K. Mehler, A. Rufinska, Angew. Chem. 96 (1984)
521; Angew. Chem. Int. Ed. Engl. 23 (1984) 534.
[S] 2, triclinic, PT(C;, No. 2), a = 11.916(6), b= 11.612(7), c=9.080(6) A,
a=68.42(4),P=85.11(5), y=62.39(4)', V = 1030(1)
Z=2,pC,,,,= l.l>
g.cm-3, F(000)=384, monochromatic MoKa radiation, A=0.71079 A,
pM,,=2.5 c m - I, specimen size ~ 0 . mm
2 (capillary); Syntex-Pi diffractometer, =2O"C, 28,.,,=45", 2024 reflections, 1276 with 1 > 2 o ( I ) , direct methods, full matrix refinement, R. R'= 0.076, 0.057 (statistical
weights). Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Energie, Physik, Mathematik
GmbH, D-7514 Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository number CSD-52260, the names of the authors, and the journal
citation.
[9] H. G. von Schnering, 0. Menge, 2. Anorg. Allg. Chem. 422 (1976) 219.
[lo) D. S . Bohle, T. C. Jones, C. E. T. Richard, W. R. Roper, J. Chem. Soc.
Chem. Commun. 1984, 865.
[ 1 I] S . M. Rocklage, R. R. Schrock, M. R. Churchill, H. J. Wasserman, Orgonometalhcs I (1982) 1332.
I121 D. S . Bohle, W. R. Roper, J . Organomet. Chem. 273 (1984) C7.
[I31 H. Schafer, D. Binder, D. Fenske, Angew. Chem. 97 (1985) 523; Angew.
Chem. I n / . Ed. Engl. 24 (1985) 522.
[ 141 Experimen/alprocedure for 6 : 5 (0.23 g, 0.42 mmol) was allowed to react
with I (0.10 g, 0.41 mmol) in 20 mL of tetrahydrofuran at ca. 20°C.
Cooling of the mixture to ca -30°C afforded green crystals of 6 I131
(0. I 5 g, 53% yield), which were washed with hexane and dried in vacuo.
Surprisingly, the corresponding reaction of K2SN2with
arsenic halides AsX, (X=Cl, Br, I) does not lead to the
expected cage compound As(NSN)~AS,even though the
analogous silicon compound, MeSi(NSN)3SiMe,'51 is
known. Instead, 3 is formed preferentially in the course of
a redox reaction.
Starting from AsBr,, compound 3 is obtained in about
40% yield as red, moderately air-stable crystals, which are
poorly soluble in hydrocarbons and diethyl ether, moderately soluble in acetonitrile, and very soluble in dichloro-
\
A',
82
0 VCH Verlagsgesellschaji mhH. 0-6940 Wernherm. 1987
.
R = fBu
3
[*] Prof. Dr. M. Herberhold, Dr. K. Guldner
Laboratorium fur Anorganische Chemie der Universitat
Universitatsstrasse 30, D-8580 Bayreuth (FRG)
Prof. Dr. A. Gieren ['I. DipLPhys. C. Ruiz-Perez, Dr. T. Hubner
Max-Planck-Institut fur Biochemie
D-8033 Martinsried (FRG)
['I Present address:
lnstitut fur Anorganische und Analytische Chemie der Universitat
Innrain 52a, A-6020 lnnsbruck (Austria)
[**I This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
0570-0833/87/0101-0082 $ 02.JO/O
Angew Chem. Int Ed. Engl. 26 11987) No I
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