SYNTHESES AND CRYSTAL-STRUCTURES OF RUTHENIUM COMPLEXES OF 1,4,8,11-TETRAAZACYCLOTETRADECANE, TRIS(2-AMINOETHYL)AMINE (TREN), AND BIS(2-AMINOETHYL)(IMINOMETHYL)AMINE - A MICROPOROUS LAYERED STRUCTURE CONSISTING OF ([K(TREN)](2)[RUCL6])(N-)(N) AND((H5O2)4[RUCL6])(N+)(N)

The second method for the synthesis of cis-[(RuCl2)-Cl-III(cyclam)]Cl (1) (cyclam = 1,4,8,11-tetraazacyclotetradecane), with use of cis-(RuC l2)-Cl-II(DMSO)(4) (DMSO = dimethyl sulfoxide) as a starting complex, is reported together with the synthesis of [Ru-II(cyclam)(bpy)](BF4)(2 ) . H2O (2) (bpy = 2,2'-bipyridine) from 1. The syntheses of Ru comple xes of tris(2-aminoethyl)amine (tren) are also reported. A reaction be tween K-3[Ru-III(ox)(3)] (ox = oxalate) and tren affords fac-[(RuCl3)- Cl-III(trenH)]Cl . 1/2H(2)O (3) (trenH = bis(2-aminoethyl)(2-ammonioet hyl)amine = monoprotonated tren) and (H5O2)(2)[K(tren)][(RuCl6)-Cl-III ] (4) as major products and gives fac-[(RuCl)-Cl-III(ox)(trenH)]Cl . 3 /2H(2)O (5) in very low reproducibility. A reaction between 3 and bpy affords [Ru-II(baia)(bpy)](BF4)(2) (6) (baia = bis(2-aminoethyl)-(imin omethyl)amine), in which tren undergoes a selective dehydrogenation in to baia. The crystal structures of 2-6 have been determined by X-ray d iffraction, and their structural features are discussed in detail. Cry stallographic data are as follows: 2, RuF8ON6C20B2H34, monoclinic, spa ce group P2(1)/c with a = 12.448(3) Angstrom, b = 13.200(7) Angstrom, c = 17.973(4) Angstrom, beta = 104.28(2)degrees, V = 2862(2) Angstrom( 3), and Z = 4; 3, RuCl4O0.5N4C6H20, monoclinic, space group P2(1)/a wi th a = 13.731(2) Angstrom, b = 14.319(4) Angstrom, c = 13.949(2) Angst rom, Beta = 90.77(1)degrees, V = 2742(1) Angstrom(3), and Z = 8; 4, Ru KCl6O4N4C6H28, trigonal, space group <R(3)over bar> with a = 10.254(4) , c = 35.03(1) Angstrom, V = 3190(2) Angstrom(3), and Z = 6; 5, RuCl2O 5.5N4C8H22, triclinic, space group <P(1)over bar> with a = 10.336(2) A ngstrom, b = 14.835(2) Angstrom, c = 10.234(1) Angstrom, alpha = 90.28 (1)degrees beta = 90.99(1)degrees, gamma = 92.07(1)degrees, V = 1567.9 (4) Angstrom(3), and Z = 4; 6, RuF8N6C16B2H24, monoclinic, space group P2(1)/c, a = 10.779(2) Angstrom, b = 14.416(3) Angstrom, c = 14.190(2 ) Angstrom, beta = 93.75(2)degrees, V = 2200.3(7) Angstrom(3), and Z = 4. Compound 4 possesses a very unique layered structure made up of bo th anionic and cationic slabs, {[K(tren)](2)[(RuCl6)-Cl-III]}(n-)(n) a nd {(H5O2)(4)[(RuCl6)-Cl-III]}(n+)(n) (n = infinity), in which both sh eets {[K(tren)](2)}(2n+)(n) and {(H5O2)(4)}(4n+)(n) Offer cylindrical pores that are occupied with the [(RuCl6)-Cl-III](3-) anions. The pres ence of a C=N double bond of baia in 6 is judged from the C-N distance of 1.28(2) Angstrom. It is suggested that the structural restraint en hanced by the attachment of alkylene chelates at the nitrogen donors o f amines results in either the mislocation or misdirection of the dono rs, leading to the elongation of the Ru-N(amine) distances and to the weakening of their trans influence. Such structural strain is also dis cussed as related to the spectroscopic and electrochemical properties of the cis-[Ru(II)L(4)(bpy)](2+) complexes (L(4) = (NH3)(4), (ethylene diamine)(2), and cyclam).