Inorg. Chem. 1982, 21, 2864-2867
2864
sulfur to give Ni(CO)(PPh,), or PPh3 to afford Ni(q2COS)(PPh3)2. A similar mechanism has been proposed for the formation of N ~ ( v ~ - C O ~ )(L ( L=) ~PEt,, P ( ~ - B U ) , )and ,~ the presence of Ni(C02)(L), has been detected spectroscopically. The complex Ni(q2-C0z)(L)2is stable, whereas similar reactions with COS afford a mixture of metal carbonyl^.^ Discussion
The stability of the species M(q2-C0S)(L), (L = PPh,) decreases in the order Pt > Pd > Ni. The platinum complex is stable in solution at low temperature, the palladium complex is stable in the solid state but decomposes upon dissolution, and the nickel complex has not been observed, although it is likely to be a transient intermediate in the observed carbonylation reaction. The reactions of ML3 complexes with COS depend on the affinity of the metal center for carbon monoxide and sulfur, the species into which COS fragments upon C--C bond cleavage. Palladium and platinum have a higher affinity for sulfur than does nickel, and the formation of dithiocarbonates is favored. Nickl(0) complexes have a high affinity for x-acceptor ligands (e.g., Ni(C0)4 is stable, Pt(CO)4 is not), and Ni(PPh3), selectively binds the CO fragment. Although the preference of the metal center for a r-acceptor rather than a a-donor ligand may be important in these reactions, kinetic factors are also important, as evidenced by the increased formation of Pt(CO)(PPh,), at higher temperature. It is interesting that Pt2S(CO)(PPh3), reacts with CS2 to
afford Pt(CS3)(PPh3)2,35but addition of CS2 to Pt(PPh3), affords P t ( ~ ~ - c s ~ ) ( P P h This , ) ~ . complex ~ is stable, and C-S bond cleavage to give Pt2S(CS)(PPh3), does not occur. Hence, it is the greater stability of the coordinated C=S bond of CS2 that prevents the formation of Pt(CS,)(PPh,), from Pt(PPh3)4 and CS2 by a pathway analogous to Scheme 111. Both Pt(S2CNR)(PPh3)2and Pt(S,CNR)(RNC)(PPh,) are formed from the reaction of Pt(PPh,), with SCNR (R = Me, Ph).41 This reaction might proceed by a mechanism analogous to the one depicted in Scheme 111. Cleavage of the dimer at both Pt-S bonds would account for the formation of both products. Acknowledgments. This work was supported by the National Science Foundation (Grant CHE80-0967 1). We thank Johnson-Matthey, Inc., Malvern, PA, for the loan of precious metal used in this study. Registry NO. Pt(COS2)(PPh3)2,25787-94-4; Pt(C02S)(PPh3)2, 8 1178-19-0; Pt($-CSZ)(PPh,)z, 15308-68-6; Pd($-COS)(P@C&CH3)3)2,8 1178-20-3; Pd(COS2)(P(p-C&CH3),)2, 81 178-21-4; Pd(v2-COS)(PPh3)2, 8 1 1 78-22-5; Pd(CO#)(P(p-C,H,CH3)3)2, 8 1 1 78-23-6; Ni(CO)(PPh3),, 15376-83-7;Ni(CO)2(PPh3)2,1300790-4; Pt($-COS)(PPh3)2, 10210-51-2; Pt#(CO)(PPh3)3,27664-43-3; Pt(PPh3)4, 14221-02-4; Pt(OZ)(PPhs)z, 15614-67-2; Pd(P@C ~ H ~ C H J )27903-26-0; ~)~, Pd(PPh3)3, 28516-49-6; Pd(OZ)(P@C&CH3)3)2, 81 178-24-7;Ni(PPh3)3,25136-46-3; cos,463-58-1. (41) Bowden, F. L.; Giles, R.; Haszeldine, R. N. J . Chem. Soc., Chem. Commun. 1974, 578.
Notes Contribution from the Departments of Chemistry, Jadavpur University, Calcutta 700032, India, and The University of Oklahoma, Norman, Oklahoma 73019 Reactions of Tetrasulfur Tetranitride [Cyclotetra(azathiene)] with Some Tin(I1) and Tin(IV) Compounds Mrinal K. Das, J. W. Bibber, and J. J. Zuckerman* Received November 13, 1981
Tetrasulfur tetranitride [cyclotetra(azathiene)] forms adducts with main-group and transition-metal Reactions in inert solvents precipitate complexes in which S4N4 acts as a mono- or bidentate ligand. In certain cases the products are adducts of disulfur dinitride. X-ray structures of S4N4.BF3,,S4N4-SbC15,4 and S4N4.AsF55show unidentate donation through the nitrogen atom. In S4N4.CuCl pairs of S4N, molecules act as bridging ligands between CuCl chains through 1,3-nitrogen atoms.6 Reaction between S4N4and SnC1, was first reported at the turn of the to give a red precipitate of stoichiometry SnC14.2S4N4,and this has been confirmed by more recent work.'O,lI The bromine analogue, SnBr4.2S4N4,forms from S4N4H4in ether or directly from S4N4in hydrocarbon solvents." Tin(I1) chloride, on the other hand, has been reported to reduce S4N4to S4N4H4in alcohol in early works or to give no reaction in ether after 48 h at room temperature." The availability of more reactive tin(I1) species such as dimethoxyltin(I1) and bis(dimethylamino)tin(II) and spec~~
*To whom correspondence should be addressed at The University of Oklahoma.
0020-1669/82/1321-2864$01.25/0
troscopic techniques such as tin-1 19m Mijssbauer spectroscopy has prompted us to reinvestigate the chemistry of S4N4and tin. Experimental Section Tetrasulfur tetranitride was prepared by the method of Jolly.I2 Anhydrous SnC12,SnBr2,and SnCI4 were obtained from Alfa Inorganics, Beverly, MA, and anhydrous SnBr, was obtained from Apache Chemicals, Rockford, IL, and used without further purification. Tin(I1) dimethoxide was prepared from SnCI2,l3and bis(dimethylamino)tin(II) was prepared by the method of Zeldin.I4 Carbon tetrachloride and dichloromethane were of reagent grade quality and were further dried over P4O10. Infrared spectra were recorded on a Beckman IR-12 spectrometer as Nujol or halocarbon mulls, and MGssbauer spectra were recorded with constant acceleration, cam-drive and Ranger Engineering instruments and were recorded vs. Ca1IgmSnO3 both as the source and standard for zero velocity at room temperature. All reactions were carried out in an inert atmosphere of dry nitrogen. Tin was determined gravimetricallyas Sn02, and halogens, nitrogen, carbon, and hydrogen were determined by
(1) Weiss, J. Fortschr. Chem. Forsch. 1966, 5, 5635. (2) Heal, H. G. Ado. Inorg. Chem. Radiochem. 1972, 15, 375.
(3) Drew, M. G. B.; Templeton, D. H.; Zalkin, A. Inorg. Chem. 1967, 6, 1906. (4) Neubauer, D.; Weiss, J. 2.Anorg. Allg. Chem. 1960, 303, 28. (5) Gillespie, R. J.; Kent, J. P.; Sawyer, J. F. Acta Crystallogr., Sect. B 1980, 836, 655. (6) Thewalt, V. Angew. Chem., Int. Ed. Engl. 1976, 15, 765. (7) Davies, 0. C. M. J . Chem. Soc. 1906, 89, 1575. (8) Wiibling, H. 2.Anorg. Allg. Chem. 1908, 57, 286. (9) Ashley, P. J.; Torrible, E. G. Can. J . Chem. 1969, 47, 2587. (10) Alange, G. G.; Banister, A. J. J . Inorg. Nucl. Chem. 1978, 40, 203. (11) Banister, A. J.; Younger, D. J . Inorg. Nucl. Chem. 1970, 32, 3763. (12) Villa-Blanco, M.; Jolly, W. L. Inorg. Synrh. 1967, 9, 98. (13) Morrison, J. S.;Haendler, H. M. J. Inorg. Nucl. Chem. 1%7,29, 393. (14) Foley, P.; Zeldin, M. Inorg. Chem. 1975, 14, 2264.
0 1982 American Chemical Society
Notes
Inorganic Chemistry, Vol. 21, No. 7, 1982 2865
Table 1. Physical Properties and Tin-119m Mossbauer and Analytical Data for the Reaction Products of S4N4with Tin Compounds Mossbauer data at 77 K, mm/s
IS
QS
r
compd SnC14.2S,N,
(r0.06) 0.45
(20.12)
(20.06) 1.39
SnBr,.2S, N,
0.75
SnCl S ,N ,
2.03
3.77
2.268
4.46
SnBr,.S,N,
2.14
3.54
Sn(OCH,),.S,N,
0.43 0.1 38
0.73
0.63d
0.82
0.60f 0.388
0.76
Sn[N(CH,), I,.S,N,
2.42 1.71" 1.93b 2.00" 2.18b 1.65" 1.32b 2.15 1.9Y 2.08b 1.50 1.52 1.74 1.2ga 1.56b
Anal. data % found (calcd) Sn 18.81 (18.87) 14.81 (14.71) 42.79 (42.13)
C1 or Br 22.65 (Cl) (22.54) 40.14 (Br) (39.61) 26.13 (Cl) (25.17)
33.01 (32.03) 43.21 (43.51) 39.71 (39.73)
color brick red
mp, "C 194-1 96
scarlet red
290-300
light orange
infusible
