J . Am. Chem. SOC.1985, 107, 3783-4785
4783
The choice of the trapping agents was limited by the lack of reactivity of 5 with nonpolar reagents and by the great lability of the silicon-carbon bond in the starting material 1. Indeed a stoichiometric amount of water or methanol readily gives rise to the formation of a new diazo product 10 in 90% yield.’* P
=si
R 2~ / > C Me
‘..Me
This lack of typical carbene reactivity and the nature of products 2-4 must be explained. The presence of an electron-rich phosphorus atom adjacent to an electron-defficient carbon suggests that delocalization of phosphine nonbonded electron pair would complete the octet of carbon and produce a dipolar species. Moreover, like phaphorus ylides, some back-bonding of the carbon electron with the phosphorus d orbital could also contribute to decrease the charge separation.
.. ..
>p-c.-
* >p=c-.
if
ct
10
In marked contrast with 1, [bis(diisopropylamino)phosphinoldiazomethane (10) is thermally unstable and rearranged under attempted distillation to give the unexpected bis(diisopropy1amin0)phosphinenitrile 11’? in 30% yield, most probably via an intermolecular reaction.
--a
10
>pzc-
Thus, it is reasonable to postulate that Xs-phosphorus compounds 2 and 3 result from 1,2-addition of the trapping agents to the phosphorus-carbon multiple bond of a “phosphorus vinyl ylide-phosphaacetylene” intermediate 5.
‘zN\
P-CEN
R 2N , ’ I1
Achnuwledgnieut. Thanks are due to A. Jacquey for technical assistance and to the CNRS for financial support. Registry No. 1, 97135-48-3; 2, 97135-50-7; 3, 97135-51-8; 4, 9713552-9; 8, 97135-53-0; 10, 97135-54-1; 11, 97135-49-4; Me,SiC(=N,)Li, 84645-45-4; (i-Pr2N),PC1, 561 83-63-2; Me,SiCl, 75-77-4; M e 2 N H , 124-40-3; M e 2 S 0 , 67-68-5.
New Chroniia Pillared Clay Catalysts Thomas J. Piiinavaia,* Ming-Shin Tzou, and Steven D. Landau
Department of Chemistry, Michigan State Universiry East Lansing, Michigan 48824 Received April 8, I985
6
The subsequent cleavage of the carbon-silicon bond in 6 was confirmed by the action of dimethylamine on the phosphorus ylide 7:’6
/H
RZN\
MazNH
I
/P-c RzN
-3
I
‘SiMes
CI
7
In the same way, mild hydrolysis of 2 led to the oxide of methylhis(diisopropy1amino)phosphorane 8,12
Me
Pillared clays are members of the smectite family of 2:l layered silicates in which the gallery cations are robust species capable of preventing the collapse of the interlayer region upon dehydration. These intercalation compounds allow a rational approach to the design of new families of microporous solids because the pores formed between the gallery cations can be systematically regulated by varying the cation size, shape, and spacing. Several types of cations have been used as pillaring agents, including alkylammonium metal ~ h e l a t e s , ~and - ~ polyoxymetal cation^.^-'^ Clays pillared by certain polyoxycations are of particular importance, because they can be converted upon dehydration and dehydroxylation to intercalates containing molecular-size oxide aggregates and protons which impart catalytically
--
8
~
( 1 ) Barrer,
Formation of sulfur ylide 4 can be rationalized by a 2 + 2 cycloaddition leading to a four-membered cyclic phosphorus ylide 9 followed by ring opening.17 ,SiMes
RzN\
- 4
RzN/(i=;
Me
O-S/ ‘Me 9
(16) Appel, R.; Schmitz, R. Chem. Ber. 1983, 116, 3521. (17) Such a mechanism has already been demonstrated in the case of sulfinylnitrene.’
0002-7863/85/1507-4783$01.50/0
_--...-l___ii_-
~-
R.M. “Zeolites and Clay Minerals as Sorbents and Molecular
Seives”; Academic Press: New York, 1978; Chapter 8. (2) (a) Mortland, M. hf.; Clementz, D. M. Clays Clay Miner. 1974, 22, 223. (b) Mortland, M. hi.; Berkheiser, V. Clays Clay Miner. 1976, 24, 60. (3) Shabtai, J.; Frydman, N.; Lazar, R. Proc. Int. Congr. Catal.,6th- 1976 1977, 660. (4) Traynor, M. F.; Mortland, hi. M.; Pinnavaia, ‘r. J. Clays Cloy Miner. 1978, 26, 318. (5) Knudson, M. 1.; McAtee, J . L. Clays Clay Miner. 1973, 21, 19. (6) Koppelman, M. H.; Dillard, J. G. Clays Clay Miner. 1980, 28, 21 1. (7) Brindley, G. W.; Sempels, R. E. Clay Miner. 1977, 12, 229. (8) Yamanaka, S.; Brindley, G. W. Clays Clay Miner. 1979, 27, 119. (9) Lahav, N.; Shani, U.; Shabtai, J. Clays Clay Miner. 1978, 26, 107. (10) Vaughan, D. E. W.; Lussier, R. J. Preprints, 5th International Conference on Zeolites, Naples, Italy, June 2-6, 1980, p 94. (11) Yamanaka, S.; Brindley, G. W. Clays Clay Miner. 1978, 26, 21. (12) Brindley, G. W.; Yamanaka, S. Am. Mineral. 1979, 64, 830. (13) Oades, J. M . CIuys Clay Mineral. 1984, 32, 49.
0 1985 American Chemical Society
4784 J . Am. Chem. SOC.,Vol. 107, No. 16. 1985
Communications to the Editor
Table I. Chromia Pillared Montmorillonites
mmole adsorbed/ge C6H6 1,3,5-Et3C6H3 (C4F9),N cmpd 9 25 O C 350 OC 500 OC (6.2)d (9.2) (10.4) I 0.48 26.8 21.0 21.0 2.04 0.75 0.43 I1 3.53 0.17 27.6 22.6 21.0 1.92 0.57 0.44 I11 1.88 0.32 16.8 14.2 13.7 61 0.37 0.03 "Prior to X-ray analysis each product was heated 2 h under Ar at the temperatures indicated. b N , BET values after dehydration in vacuo at 350 O C for 3 h.
