Crystal and molecular structure of dinitrosylbis(triphenylphosphine)rhodium perchlorate, [Rh(NO)2(P(C6H5)3)2][ClO4] (original) (raw)
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Polyhedron, 1987
The pentacoordinate rhodium nitrosyl complexes [RhBr,(NO)L j [L = P(OPh),Ph, P(OMe)Ph2 or P(OPr')Phd have been synthesized and the structures of [RhBr, (NO)(P(OMe)Ph,}7_ and [RhBr,(NO){P(OPr')Ph,),] have been determined X-ray crystallographically. Both of these latter compounds are tetragonal pyramidal with the nitrosyl group apical. The methoxydiphenylphosphine ligands in [RhBr,(NO){P(OMe)Ph,} 2] are c&disposed whereas the larger cis-propoxydiphenylphosphine ligands in [RhBr,(NO) {P(OPI)Ph,) 2] are mutually trans. The nitrosyl group in frans-[RhBr,(NO)(P(OPI)Ph,) 2] eclipses an Rh-P axis but in cis-[RhBr2(NO){P(OMe)Ph2)z] it is staggered with respect to the P-Rh-P linkage. The isomeric behaviour of nitrosyl complexes of type [RhX,(NO)LJ (X = halogen, L = phosphorus donor ligand) is rationalized in terms of the size of the ligand L. deviations in parentheses Rh-Br( 1) Rh-Br(2) Rh-P( 1) F&-P(2) Rh-N N--o(3) P(lFx1) P(lW(l1) P(lW(21) 0(1)-W) P(2W(2) P(2~(31) P(2W(41) 0(2)-c(2) Br( l)-Rh-Br(2) Br(l)-Rh-P(1) Br( 1 )-Rh-P(2) Br( l)-Rh-N Br(2)-Rh-P( 1) Rh-Br Rh-P Rh-N N-O(l) P--o(2) P-qll) P-c(21) 0(2)-v) C(lW(2) C(lW(3) Br-Rh-Br' Br-Rh-P Br-Rh-N
Rhodium and ruthenium tetracarboxylate nitrosyl complexes: Electronic structure and metal-metal bond
Russian Journal of Coordination Chemistry, 2007
Among binuclear tetracarboxylate rhodium and ruthenium complexes å 2 ( µ -O 2 CH ) 4 ( L ) 2 and related compounds with other bridging ligands, a special place is occupied by complexes with coordinated nitric oxide. The structural characteristics of dinitrosyl complexes å 2 ( µ -O 2 CR ) 4 ( NO ) 2 (M = Ru, Rh; R = alkyl or CF 3 ) [1, 2] differ markedly from characteristics of related compounds with other ligands: the M-M distance in the ruthenium tetracarboxylates is usually 2.28 Å, that in rhodium tetracarboxylates with axial N-donor ligands L is ~2.4 Å, while in å 2 ( µ -O 2 CR ) 4 ( NO ) 2 , this distance exceeds 2.5 Å and almost coincides for M = Ru, Rh. Moreover, whereas other Ru 2 ( µ -O 2 CR ) 4 ( L ) 2 complexes have a triplet ground state, the ground state of M Ru 2 ( µ -O 2 CR ) 4 ( NO ) 2 is singlet. The metal-metal bond order in å 2 ( µ -O 2 CR ) 4 and M 2 ( µ -O 2 CR ) 4 ( L ) 2 dimers with usual ligands L is dictated, first of all, by the nature and the formal oxidation state of the metal (which is determined by known rules [3]).
Organometallics, 1998
Treatment of RuCl 2 (PPh 3 ) 3 and RuHCl(PPh 3 ) 3 with the tin compound CH 2 C(Me)CHC(Me)CH 2 SnMe 3 gives the corresponding acyclic pentadienyl halfsandwich (η 5 -CH 2 C(Me)CHC(Me)CH 2 )RuX(PPh 3 ) 2 [X = Cl, (2); H, ]. The steric congestion in 2 is most effectively relieved by formation of the cyclometalated complex (η 5 -CH 2 C(Me)CHC(Me)CH 2 )Ru(C 6 H 4 PPh 2 )(PPh 3 ) (4). Addition of 1 equiv of PHPh 2 to (η 5 -CH 2 CHCHCHCH 2 )RuCl(PPh 3 ) 2 (1) affords the chiral complex (η 5 -CH 2 CHCHCHCH 2 )RuCl(PPh 3 )(PHPh 2 ) (5), while compound (η 5 -CH 2 C-(Me)CHC(Me)CH 2 )RuCl(PPh 3 )(PHPh 2 )] (6) is directly obtained from the reaction of RuCl 2 (PPh 3 ) 3 with CH 2 C(Me)CHC(Me)CH 2 Sn(Me) 3 and PHPh 2 . Treatment of RuCl 2 (PPh 3 ) 3 with the corresponding Me 3 SnCH 2 CHCHCHNR (R = Cy, t-Bu) affords (1-3,5-η-CH 2 CHCHCHNCy)RuCl(PPh 3 ) 2 (7) and [1-3,5-η-CH 2 CHCHCHN-(t-Bu)]RuCl(PPh 3 ) 2 (8). The hydrolysis of 7, on a silica gel chromatography column, allows the isolation of RuCl(η 5 -CH 2 CHCHCHO)(PPh 3 ) 2 (9). The azapentadienyl complex 7 reacts with 1 equiv of PHPh 2 to afford [1-3,5-η-CH 2 CHCHCHN(Cy)]RuCl(PPh 3 )(PHPh 2 ) (10), while the corresponding product [1-3,5-η-CH 2 CHCHCHN(t-Bu)]RuCl(PPh 3 )(PHPh 2 ) (11) from 8 is only observed through 1 H and 31 P NMR spectroscopy as a mixture of isomers. Two equivalents of PHPh 2 gives spectroscopic evidence of [η 3 -CH 2 CHCHCHN(t-Bu)]-RuCl(PHPh 2 ) 3 . A mixture of products [η 5 -CH 2 C(Me)CHC Me)O]RuCl(PPh 3 ) 2 (12) and [η 5 -CH 2 C(Me)CHC(Me)O]RuH-(PPh 3 ) 2 (13) is obtained from reaction of RuCl 2 (PPh 3 ) 3 with Li[CH 2 C(Me)CHC(Me)O]. In contrast, the oxopentadienyl compound 13 is cleanly formed from RuHCl(PPh 3 ) 3 and Li[CH 2 C(Me)CHC(Me)O]. An attempt to separate compounds 12 and 13 by crystallization gives an orthometalated product [η 5 -CH 2 C(Me)CHC(Me)O]Ru(C 6 H 4 PPh 2 )(PPh 3 ) , which is the oxopentadienyl analogue to 4. The bulky [1-3,5-η-CH 2 C(t-Bu)CHC(t-Bu)O]RuH(PPh 3 ) 2 (15) analogue to 13 has also been prepared from RuHCl(PPh 3 ) 3 and Li[CH 2 C(t-Bu)CHC(t-Bu)O]. Compounds 3, 5, 6, 7, and 12−15 have been structurally characterized. The preferred heteropentadienyl orientations and the relative positions of the H, Cl, PPh 3 , and PHPh 2 ligands have been established in the piano-stool structures for all compounds, and it can be definitively surmised that the chemistry involved in the heteropentadienyl halfsandwich compounds studied is dominated by steric effects.
Inorganic Chemistry, 1975
The structures of RuCh(NO)(P(C6H5)3)2 and R u C~~C~-N N C~H~C H~) (P (C~H~)~)~~C~~~~~~ have been determined crystallographically. Both complexes possess a similar pseudooctahedral geometry with trans phosphine ligands and meridional chloro ligands. The short RuN and N-X (X = 0, N) distances suggest that both nitrosyl and aryldiazo ligands are good K acceptors; however, subtle but distinct differences in the two ligands suggest that NO is the better T acceptor. The much greater steric bulkiness of the aryldiazo ligand has a pronounced effect on the intramolecular interactions within the complex and on the three-dimensional packing of the complex in the solid state. Both RuN -X angles are essentially linear. The iX(l)-N(2)-C(phenyl) angle at 137.1 (5)' in the diazo complex is unusually large. The Ru-Cl(trans to N) distances compared with the Ru-Cl(trans to CI) distances are shortened by 0.041 (3) A in the nitrosyl complex and by 0.008 (3) A in the diazo complex. Both compounds are considered to be Ru(I1) complexes of NO+ or NNAr+, with the respective ligands acting as three-electron donors. The nitrosyl complex crystallizes from dichloromethane-methanol as solvent-free crystals in space group Czh6-12/a with a = 15.877 (3) A, b = 9.540 (2) A, c = 22.326 (4) A, / 3 = 102.79 (l)', and 2 = 4. Each molecule has imposed C2 symmetry. On the basis of 2671 unique reflections with F o~ > 3u(F02), the structure was refined by full-matrix, least-squares methods to R = 0.058 and RW = 0.068. Some important molecular parameters are RuN = 1.737 (7) A, K-0 = 1,142 (8) A, and RuN -0 = 180.0'. The tolyldiazo complex crystallizes from dichloromethane as solvated crystals in space group C2h5-P21/C with a = 12.406 (8) A, b = 18.421 (13) A, c = 18.565 (13) A, p = 93.05 (l)', and Z = 4. The molecule has no imposed symmetry, but approximates Cs symmetry. On the basis of 5100 unique reflections with Fo2 > 3u(Fo2), the structure was relined by full-matrix, least-squares methods to R = 0.058 and Rw = 0.067. Some important molecular arameters in the diazo complex are Ru-N(1) = 1.784 (5) A, N(l)-N(2) = 1.158 (6) A, N(Z)-C(phenyl) = 1.376 (6) 1 , and Ru-N(1)-N(2) = 171.9 (5)'. Both structures consist of discrete monomeric molecules of the respective complex. The values of u(N0) and v(NN) for these and other nitrosyl and aryldiazo complexes are discussed, and some empirical rules are suggested for distinguishing between bent and linear nitrosyl ligands and between doubly bent and singly bent aryldiazo ligands on the basis of the N-0 and N-N stretching frequencies. The syntheses of [M(NO)(diphos)2] [PFs]z (M = Rh, Ir) are reported
Inorganic Chemistry, 1975
The structure of dinitrosylbis(triphenylphosphine)osmium(-11) hemibenzene, OS(N~)Z(P(C~H~)~)Z.'/~C~H~, has been determined using three-dimensional X-ray diffraction techniques. This structure completes those of-M(No)z(P(Cf,Hs)3)2 of the Fe triad. The conditions and requirements leading to bent and linear nitrosyl ligands in four-coordinate complexes are discussed and compared with those for similar five-and six-coordinate complexes. A set of empirical rules is presented which allows the a priori prediction in many cases of whether the bent or linear form of the nitrosyl ligand will be present. The Os compound crystallizes from benzene-hexane as hemisolvated crystals in space group Czhj-P21/n with four formula units in a cell of dimensions a = 17.034 (5) A, b = 18.735 (5) A, c = 10.799 (3) A, and / 3 = 96.81 (1)O. Based on 3455 unique reflections with F.2 > 30(F02), the structure was solved and refined by full-matrix, least-squares methods to values of R of 0.031 and RW of 0.039. The structure consists of discrete molecules of the complex and of benzene, the latter being located on centers of inversion. The osmium complex is four-coordinate with pseudotetrahedral geometry and linear nitrosyl ligands. Although ESCA spectra show that the nitrosyl ligands are very effective at removing electron density from the metal, the coordination gecmetry is best rationalized on the basis of Os(-II), which is a dlo system. This structure is remarkably similar to its Ru analog. The short Os-N and N-0 distances point to the extensive metal-nitrogen and nitrogen-oxygen multiple bonding. Important angles and distances are Os-N(l) = 1.771 (6) A, Os-N(2) = 1.776 (7) A, ?J(1)-0(1) = 174.1 (6) O , and P(l)-Os-P(2) = 103.51 (6)' 1.195 (8) A, N(2)-O(2) = 1.211 (7) A, N(I)-Os-N(2) = 139.1 (3) O , 0~-N (l)-O (l) = 178.7 (7)O, Os-N(2)-0(2) =
Inorganic Chemistry, 1999
The reaction of the dinuclear [RuCl 2 (dppb)] 2 (µ-dppb) (dppb ) 1,4-bis(diphenylphosphino)butane) with Cl 2 in MeOH for ∼30 min at room temperature gives the bright-red solid mer-RuCl 3 (dppb)(H 2 O) (1); Cl 2 treatment for ∼10 min affords the red-brown, mixed valence complex [RuCl(dppb)] 2 (µ-Cl) 3 (2). Controlled bulk coulometric reduction of 50% of the content of a CH 2 Cl 2 solution of 1 also produces 2, formed by the reaction of 1 with "RuCl 2 (dppb)" produced in situ during the electrolysis. Complexes 1 and 2 were characterized by spectroscopic techniques [including electron spin resonance (ESR)], magnetic moments and cyclic voltammetry, and the structure of 1 was determined by X-ray diffraction. The structure shows that the aquo ligand forms hydrogen bonds with two cis-chlorine ligands of the neighboring molecule of the complex; this interaction gives rise to exchange coupling between two Ru(III) centers that is reflected in the ESR spectrum. A species 3 analogous to 1 has been obtained with the diop ligand [diop ) (2R,3R)-or (2S,3S)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane], on using RuCl 2 (diop)(PPh 3 ) or [RuCl(diop)] 2 (µ-Cl) 3 as precursors. The RuCl 3 (P-P)L complexes (P-P ) dppb, diop; L ) dimethyl sulfoxide, MeOH) are readily synthesized from 1 or 3. (1) ) Queiroz, S. L.; Batista, A. A.; Oliva, G.; Gambardella, M. T. do P.; Santos, R. H. A.; MacFarlane, K. S.; Rettig, S.
Tetradentate bis-phosphine ligands (P2N2 and P2S2) and their Rh(III), Ni(II) and 105Rh Complexes: X-ray crystal structures of trans-[RhCl2(L2)]PF6, Ni(L2)2 and μ-O2SO2-[Ni(L5)]2(PF6)2
Nuclear Medicine and Biology, 2011
Introduction: Tetradentate acyclic and macrocyclic diphosphine ligands (P 2 N 2 and P 2 S 2) have been synthesized and characterized as potential chelates for Rh(III). Methods: The coordination complexes [RhCl 2 (L1)]Cl, trans-[RhCl 2 (L2)]PF 6 , [Ni(L2)](PF 6) 2 , [Ni(L3)](PF 6) 2 , [RhCl 2 (L4)]PF 6 and [RhCl 2 (L5)]PF 6 have been synthesized and characterized. In addition, radiochemistry studies of the 105 Rh complexes with the ligands N,N′-bis[2-(diphenylphosphino)phenyl]-1,3-diaminopropane (L1), 4,8-diphenyl-1,11-diaza-4,8-diphosphaundecane (L2), 5,9-diphenyl-5,9-diphospha-2,12-dithiatridecane (L3) and 1,4,8,11-tetraphenyl-4,8-diphospha-1,11-dithiaundecane (L4) are reported, including normal mouse biodistributions of 105 Rh-L2. Results: trans-[RhCl 2 (L2)]PF 6 crystallized in the monoclinic space group P2 1 /c with a=9.9353(5) Å, b=9.0929(5) Å, c=28.689(1) Å, β=93.1400(10) deg, Z=4, R=0.037 and R w =0.053. [Ni(L2)](PF 6) 2 crystallized in the monoclinic space group P2 1 /c with a=11.9665(6) Å, b=14.8903(7) Å, c=31.148(1) Å, β=91.587(1) deg, Z=8, R=0.056 and R w =0.083. μ-O 2 SO 2-[Ni(L5)] 2 (PF 6) 2 , an unusual sulfate-bridged Ni (II) dimer, crystallized in the triclinic space group P1 bar with a=15.179(2) Å, b=15.514(2) Å, c=16.128(2) Å, α=105.280(7) deg, β=113.074(6) deg, γ=101.657(8) deg, Z=2, R=0.050 and R w =0.072. Conclusions: Phosphine-containing ligands allowed for lower temperatures and lower ethanol concentrations in the formulations for 105 Rh (L) complexation, but at the expense of higher ligand concentrations.
Journal of The Chemical Society-dalton Transactions, 1997
The reaction of [RuCl 2 (dippe) 2 ] [dippe = 1,2-bis(diisopropylphosphino)ethane] with NaBPh 4 in MeOH afforded the red-brown five-co-ordinate complex [RuCl(dippe) 2 ][BPh 4 ] 1. In analogous fashion, the complex cis-[OsCl 2 (dippe) 2 ] 2, prepared by reaction of [NH 4 ] 2 [OsCl 6 ] with dippe in refluxing 2-methoxyethanol, yielded the corresponding five-co-ordinate species [OsCl(dippe) 2 ][BPh 4 ] 3 upon treatment with NaBPh 4 in MeOH. Both complexes 1 and 3 react with PhSH furnishing the five-co-ordinate benzenethiolato derivatives [Ru(SPh)(dippe) 2 ][BPh 4 ] 4 and [Os(SPh)(dippe) 2 ][BPh 4 ] 5 respectively. The crystal structure of 4 has been determined, and shows that the complex cation adopts a distorted trigonal-bipyramidal geometry. With the exception of 4, which is rigid on the NMR time-scale, the other five-co-ordinate complexes are stereochemically non-rigid, and in some instances undergo dynamic processes in solution which have been ascribed to interactions with the solvent. Whereas complexes 1 and 5 do not react with H 2 , addition of H 2 to 3 yields the dihydrogen complex trans-[OsCl(H 2 )(dippe) 2 ][BPh 4 ] 6. The reaction of 4 with H 2 afforded the known five-co-ordinate hydride complex [RuH(dippe) 2 ][BPh 4 ], formed presumably by elimination of HSPh from an unstable thiolate-dihydrogen (or