Organometallic polymers assembled from cation-pi interactions: use of ferrocene as a ditopic linker within the homologous series [{(Me3Si)2NM}2.(Cp2Fe)]infinity (M=Na, K, Rb, Cs; Cp=cyclopentadienyl).
Addition of ferrocene to solutions of alkali metal hexamethyldisilazides M(HMDS) in arenes (in which M=Na, K, Rb, Cs) allows the subsequent crystallization of the homologous series of compounds [{(Me(3)Si)(2)NM}(2) (Cp(2)Fe)](infinity) (1-4). Similar reactions using LiHMDS led to the recrystallization of the starting materials. The crystal structures of 1-4 reveal the formation of one-dimensional chains composed of dimeric [{M(HMDS)}(2)] aggregates, which are bridged through neutral ferrocene molecules by eta(5)-cation-pi interactions. In addition, compounds 3 and 4 also contain interchain agostic M--C interactions, producing two-dimensional 4(4)-nets. Whereas 1 and 2 were prepared from toluene, the syntheses of 3 and 4 required the use of tert-butylbenzene as the reaction media. The attempted crystallization of 3 and 4 from toluene resulted in formation of the mixed toluene/ferrocene solvated complexes [{(Me(3)Si)(2)NM)(2)}(2) (Cp(2)Fe)(x)(Tol)(y)](infinity) (in which M=Rb, x=0.6, y=0.8, 5; M=Cs, x=0.5, y=1, 6). The extended solid-state structures of 5 and 6 are closely related to the 4(4)-sheets 3 and 4, but are now assembled from a combination of cation-pi, agostic, and pi-pi interactions. The charge-separated complex [K{(C(6)H(6))(2)Cr}(1.5)(Mes)][Mg(HMDS)(3)] (15) was also structurally characterized and found to adopt an anionic two-dimensional 6(3)-network through doubly eta(3)-coordinated bis(benzene)chromium molecules. DFT calculations at the B3 LYP/6-31G* level of theory indicate that the binding energies of both ferrocene and toluene to the M(HMDS) dimers increases in the sequence Li<Na<K. This pattern is a consequence of the larger metals allowing more open coordination spheres to support cation-pi contacts. By comparison, binding of the isolated metal cations to the aromatic groups follow the reverse order K<Na<Li. A combined analysis of theoretical and experimental data suggest that ferrocene is a stronger cation-pi donor than toluene for the lighter metals, but that this difference is eliminated on descending the group.
Morris
J Jacob
JJ
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556-5670, USA.
Noll
Bruce C
BC
Honeyman
Gordon W
GW
O'Hara
Charles T
CT
Kennedy
Alan R
AR
Mulvey
Robert E
RE
Henderson
Kenneth W
KW
D002412:Cations / Q000737:chemistry; D003198:Computer Simulation; D018360:Crystallography, X-Ray; D003517:Cyclopentanes / Q000737:chemistry*; D005296:Ferrous Compounds / Q000737:chemistry*; D000075163:Metallocenes; D008672:Metals, Alkali / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry*; D012680:Sensitivity and Specificity; D013055:Spectrophotometry, Infrared / Q000379:methods; D013237:Stereoisomerism
D002412:Cations; D003517:Cyclopentanes; D005296:Ferrous Compounds; D000075163:Metallocenes; D008672:Metals, Alkali; D009942:Organometallic Compounds; D011108:Polymers; C004998:ferrocene