O)(2)(PH(2)P(CH2CH2O)(N)CH(2)CH(2)PPH(2)-P,P')](M) (N=4, 5, M=1,2,...) METALLACROWN X-RAY CRYSTAL-STRUCTURES OF 2(CO)(2)(PH(2)P(CH2CH2O)(4)CH(2)CH(2)PPH(2)-P,P'), A COMPLEX WHICH EXHIBITS ROTATIONAL ISOMERS INTHE SOLID-STATE AND -(MU-PH(2)P(CH2CH2O)(4)CH(2)CH(2)PPH(2)-P,P')](2), AN UNUSUAL DIMETALLACROWN ETHER

The reactions of Ph(2)P(CH2CH2O)(n)CH(2)CH(2)PPh(2) (n = 4, 5) ligands with RuCl2(CO)(3)(THF) give a variety of complexes of the type 2(CO)( 2){Ph(2)P(CH2CH2O)(n)CH2CH2-PPh(2)-P,P'}](m) Multinuclear NMR and IR s pectroscopic studies indicate that the major product in each reaction is the mononuclear (m = 1) complex in which the Ph(2)P(CH2CH2O),(n)-CH (2)CH(2)PPh(2) ligand spans two trans positions. The minor products ar e polynuclear (m 2, 3,...) complexes in which each Ph(2)P(CH2CH2O)(n)C H(2)CH(2)PPh(2) ligand bridges two rutheniums. X-ray crystal structure s of s,cis,trans-RuCl2(CO)(2){Ph(2)P(CH2CH2O)(4)CH2CH2- PPh(2)-P,P'}, 4a, (monoclinic space group P2(1)/n, a = 10.194(1), b = 22.907(3), c = 15.259(2) Angstrom; beta = 92.46(1)degrees; V = 3560.0(8) Angstrom(3) : Z = 4) and [cis, cis,trans-RuCl2(CO)(2){mu-Ph(2)P(CH2CH2O)(4-) CH(2) CH(2)PPh(2)-P,P'}](2).(CH3)(2)CO, 4b.(CH3)(2)CO, (monoclinic space gro up P2(1)/a, a 18.976(3), b = 22.076(5), c = 10.426(8) Angstrom; beta = 111.64(1)degrees; V = 4060(1) Angstrom(3); Z = 4) confirm these concl usions. The monomeric 4a is a rare example of an octahedral complex wi th a trans-spanning bis(phosphine) ligand. Two different rotamers of 4 a are observed in the solid state. In the major rotamer the trans-span ning ligand passes between one chloride and one carbonyl while in the minor rotamer the trans-spanning ligand passes between the two chlorid es. The dimeric 4b is the first example of a dimetallacrown ether. The trans phosphines in 4b cause the formation of two, distinct metallacr own ether sites separated by a chloride and a carbonyl ligand on each ruthenium.