Znorg. Chem. 1994, 33, 434-443
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Using Phosphohydrazides as Building Blocks to Multiredox Polymetallic Compounds Containing Ferrocenyl Groups. Electrochemical and NMR Behaviors in Solution BBatrice Delavaux-Nicot, RenB Mathieu,' Dominique de Montauzon, Guy Lavigne, and Jean-Pierre Majoral Laboratoire de Chimie de Coordination du C N R S , U P 8241 l i k par conventions a 1'UniversitC Paul Sabatier et a I'Institut National Polytechnique, 205 route de Narbonne, 3 1077 Toulouse Cedex, France
Received May 12, 1993" The condensation of phosphodi- or phosphotrihydrazides Ph3-nP(X)[N(CH3)NH2], (la (n = 2; X = S); l b (n = 2; X = 0); 2a; (n = 3; X = S); 2b (n = 3; X = 0))with ferrocenecarbaldehyde is a high-yield synthetic route to new ferrocenyl phosphohydrazoneligands Ph,P(X) [N(CH~)N=CHCSH~F~(CSH~)] 3-n (a, 3b, 4a, 4b). The structure of 3b has been solved by X-ray crystallography. Crystal data at room temperature are a = 15.176(1)& b = 15.170(2)& c = 12.533(2)& 6 = 106.582(8)O, Z = 4 for a monoclinic system, space group P21/c, V = 2765.5(5) A3,Z = 4; R = 0.049, R , = 0.056 for 2104 observations and 361 variable parameters. Similar phenyl thiophosphodiand trihydrazones 6 and 7 were obtained by condensation with benzaldehyde. Depending on the ligand/copper(I) ratio la, 3a, or 6 led to [LCu]z[SO3CF3]2 or [ L ~ C U ] [ S O ~ Ccomplexes. F~] For the 1/1 adducts the sulfur atom of the PS group bridges the two copper centers and the P-N-N arms of each ligand are coordinated to two different copper atoms. For the 2/ 1 adducts each ligand is bonded by the sulfur and one P-N-N arm, and in solution, NMR gives evidence of an exchange phenomenon between the free and complexed P-N-N arms. The ligand 4a is a bidentate ligand through the sulfur atom with one of the P-N-N arms toward CuCl and a tridentate one through the P-N-N arms toward CuS03CF3. Condensation reactions between ferrocenecarbaldehydeand the complexes of l a led to the similar complexes containing the ligand 3a. Electrochemical studies of the ligands containing the ferrocenyl moieties and their complexes show that complexation induces, as expected, a shift toward more anodic potential. For the [(3a)*Cu][S03CF3] complex, two waves corresponding to the two different ferroceneenvironments have been observed.
Introduction After the important work of Lehn and his group concerning the design of receptors for small organic molecules,' Constable explained in a recent paper how metallic sandwiches could bring a new element to molecular recognition.2 The use of appropriate acyclic ferrocene derivatives in this field could have many advantages and a wide field of applications in chemistry, physics, and biology. For instance in an approach toward new technologies, they can be used for the constitution of membranes, micellars, or other supramolecular assemblies, for the design of molecular switches or sensors, in which a change in the redox potential of the ferrocene unit is triggered by an alkali metal ion binding for instance. Specifically, Beer ef al. have been interested in the design of such molecules and have extended this study to macrocyclic compounds3and recently to anion acyclic receptors containing cobaltocenium moieties4 Recently one of us has shown that phosphohydrazides RP(X)[N(CH3)NH2]2 (X = 0,S;R = Ph) are well adapted to the building of macrocycles by condensation with various functionalized dialdehyde~.~ With the aim of synthesizing, according to the same strategy, phosphorus-containingmacrocyclespossessing some of the afore mentioned properties, we have chosen in a first approach to condense ferrocenecarbaldehyde with phosphohydrazides and to check their coordinationproperties. Indeed these Abstract published in Aduance ACS Abstracts, December 15, 1993. (1) See, for example: Lehn, J. M. Angew. Chem., Int. Ed. Engl. 1988, 27, 89. (2) Constable, E. C. Angew. Chem., Int. Ed. Engl. 1991, 30, 407 and @
references therein. (3) See, for example: (a) Beer, P. D. Chem. SOC.Rev. 1989, 409 and
references therein. (b) Beer, P. D.; Keefe, A. D.; Slawin, A. M. Z.; Williams, D. J. J. Chem. SOC.,Dalton Trans. 1990,3675. (c) Beer, P. D.; Tite, E. L.; Ibboston,A. J. Chem. Soc., Dalton Trans. 1991, 1691. (d) Beer, P. D.; Kocian, 0.;Mortimer, J. R.; Spencer, P. J . Chem. Soc., Chem. Commun. 1992,602. (4) Beer, P. D.; Hesek, D.; Kodacova, J.; Stokes, S. E. J . Chem. SOC.,Chem. Commun. 1992, 270.
ligands contain several binding sites due to the presence of two types of nitrogendonor sites and the heteroatomx. Surprisingly, results about complexing properties of phosphorus hydrazides are sparse: Recently Engelhardt et al. have studied the formation of complexes between phosphoric acid hydrazides and Cd(I1) or Ni(I1) salts. Dimeric and polymeric structures have been obtained' in which the chelating ligands are N-bonded or N- and S-bonded. Katti et al. also reported on the potentialities of functionalized phosphorus hydrazides as novel chelating ligands for Co(I), Cu(I), and Pd(I1) complexation.* In a previous paper, we described the synthesis and characterization of the first example of a derivative possessing ferrocenylhydrazone and thiophosphanyl moieties9 which shows a remarquable ability to give a dicopper complex. In this paper we (5) (a) Majoral,J.-P.; Badri, M.; Caminade, A,-M.;Delmas, M.; Gaset, A. Inorg. Chem. 1988,27,3873. (b) Majoral,J.-P.; Badri, M.; Caminade,
A.-M.; Gorgues,A.; Delmas, M.; Gazet, A. Phosphorus SulfurSilicon 1990, 49-50, 143. (c) Badri, M.; Majoral, J.-P.; Caminade, A.-M.; Delmas, M.; Gaset, A.; Gorgues, A.; Jaud, J. J . Am. Chem. Soc. 1990, 112,5618. (d) Badri, M.; Majoral, J.-P.;Gonce, F.; Caminade, A.-M.; SallC, M.; Gorgues, A. Tetrahedron Letr. 1990,31,6343. (e) Majoral, J.-P.; Badri, M.; Caminade,A.-M.;Delmas,M.; Gaset, A. Inorg. Chem. 1991,30,344. ( f ) Majoral,J.-P.;Badri, M.;Caminade, A.-M.Hereroar. Chem. 1991, 2, 45. (g) Gonce, F.; Caminade, A.-M.; Majoral, J.-P. Tetrahedron Letr. 1991, 32, 203. (h) Gonce, F.; Caminade, A.-M.; Boutonnet, F.; Majoral, J.-P. J . Org. Chem. 1992,57, 970. (i) Goncc, F.; Caminade, A.-M.;Majoral, J.-P.; Jaud, J.; Vignaux, P. Bull. SOC. Chim. Fr. 1992,129, 237. 6)Colombo-Khater,D.; Caminade, A. M.; Delavaux-Nicot, B.; Majoral, J. P. Organometallics 1993, 12, 2861. (6) (a) Casteran-Baumassy,J.; Dagnac, P.;Gleizts, A. J . Chem. Res. Synop. 1979, 164; J. Chem. Res. Miniprint 1979,2129-2166. (b) Dagnac, P.; Casteran-Baumassy, J. J . Mol. Strucr. 1980, 62, 157. (c) Turpin, R.; Casteran-Baumassy,J.; Dagnac, P. J. Chem. Res. Synop. 1980, 138; J . Chem. Res. Miniprint 1980, 2074. (d) Engelhardt, U.; Friedrich, B.; Stronburg, B. Acta Crystallogr. 1982, 838, 753. (e) Engelhardt,U.; Friedrich, B.;Kirner, I. Z. Naturforsch. 1981,368, 791. (f) Engelhardt, U.; Renz-Kreikebohn, C. Acta Crystallogr. 1989, C45, 1679. (7) Engelhardt,U.;Renz-Kreikebohm,C.;Stronburg,B. Phosphorus,Sulfur Silicon 1993, 77, 266. (8) Katti, V. K.; Singh, P. R.; Barnes, C. L. Inorg. Chem. 1992,31,4588.
0020-166919411333-0434$04.50/0 0 1994 American Chemical Society
Inorganic Chemistry, Vol. 33, No. 3, 1994 435
Phosphohydrazides as Building Blocks (353)
Table 1. Interatomic Distances (A) and Angles (deg) for PhP(O)(NMeNCH=Fc), (3b), with Esd's in Parentheses
P-o(1) P-N(i) N(1)-N(2) N(1)-CU ) N(2)-C(2) C(l)-C(ll) Fe(l)-C(ll) Fe( 1)-C(12) Fe(l)-C(13) Fe( 1)-C( 14) Fe(l)-C(15) Fe( l)-C(2 1) Fe( l)-C( 22) Fe( 1)-C(23) Fe( 1)-C(24) Fe(l)-C(25) Figure 1. Perspectiveviewof thecomplexPhP(O)[N(CH3)N=CHCsH4Fe(CsHs)]2 (3) Thermal . ellipsoids are shown at the 50% probability level.
1.466(6)
Fe-CpI Linkage 2.045(8) Fe(2)-C(31) 2.024(9) Fe(2)-C(32) Fe(2)-C(33) 2.01(1) Fe(2)-C( 34) 2.02(1) 2.02( 1) Fe(2)-C(35) 2.03( 1) Fe(2)-C(41) 2.01(1) Fe(2)-C(42) Fe(2)-C(43) 2.02(1) Fe(2)-C(44) 2.01 (1) Fe(2)-C(45) 2.04(1)
1.791(9) 1.664(7) 1 j 1.27(1) 1.45(1) 1.45(1) 2.046(9) 2.04(1) 2.02( 1) 2.033(8) 2.036(7) 2.02(1) 2.02( 1) 2.03(1) 2.033(9) 2.04( 1)
Cyclopentadienyl Rings 1.43(1) C( 1I)
