Encapsulation of Triphenylene Derivatives in the Hexanuclear Arene Ruthenium Metallo-Prismatic Cage [Ru6(p-PriC6H4Me)6(tpt)2(dhbq)3]6+ (tpt = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine, dhbq = 2,5-dihydroxy-1,4-benzoquinonato) (original) (raw)
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Organometallics, 1994
Reaction of CpRuCl(iPr-DAB) (1) with AgOTf(AgCF3S03) in THF and subsequent addition of L (L = ethene (a), propene (b), cis-2-butene (c), dimethyl maleate (d), dimethyl fumarate (e), fumaronitrile (f), acetylene (i), dimethyl acetylenedicarboxylate (DMAC) Q), CO (11, pyridine (m), triphenylphosphine (n)) led to the ionic complexes [CpRu(iPr-DAB)(L)l[OTfl 2a-f,ij,l-n, respectively. For trans-2-butene (g) and 2-methylpropene (h), no coordination complex was formed. Addition of methyl propiolate (HC4X!(O)OCH3, k) to [CpRu(iPr-DAB)l[OTfl resulted in [ C~R U (~P~-D A B ) (~~-H C~C C ( O ) O C H~) I [ O T~~ (2k) and 21 in a 4:l ratio. An X-ray structure determination on 2b was carried out. Crystal data for 2b: triclinic, space group Pi with a = 9.0649(6) A, b = 9.6151(6) A, c = 13.0099(6) A, a = 94.322(6)", j3 = 104.258(8)", y = 98.977(6)", 2 = 2, final R = 0.033. Surprisingly, the structure shows the propene y2-coordinated to the metal center with the methyl group pointing toward the cyclopentadienyl ring. Nucleophilic attack of OCH3-on [CpRu(iPr-DAB)(q2-dimethyl maleate)l[OTfl (2d) at 20 "C led to two diastereomers of CpRu(iPr-DAB)CH(C(O)OCH3)-CH(OCHd(C(O)OCH3) (3) in a 97:3 ratio. Reaction of [CpRu(iPr-DABXy2-DMAC)1[OTfl (2j) with -0CH3 at 20 "C yielded CpRu(iPr-DAB)OCHs (61, whereas reaction at -40 "C gave 6 (30%) and C~RU(~P~-DAB)C(C(O)OCH~)=C(OCH~)(C(O)OCH~) (4; 70%). Reaction of 2d with NH2iPr and NHiPr2 as the nucleophiles yielded the substitution products [CpRu(iPr-DAB)(NH2iPr)l[OTfl (2p) and [CpRu(iPr-DAB)(NHiPrz)I[OTfl (2q), respectively. Complex 2j reacted with NHziPr to form 2p, whereas 2j was inert to substitution with NHiPr2.
Organometallics, 2006
The cationic N-heterocyclic carbene (NHC) rhodium complexes [Rh(NHC) 3 (CO)] + (NHC) ICy (1), I i Pr 2 Me 2 (2)) have been isolated from the reactions of RhH(PPh 3) 3 (CO) with the free NHCs. The hexafluorophosphate salts of both compounds, 1[PF 6 ] and 2[PF 6 ], have been characterized by X-ray diffraction. The observed temperature dependences of the 1 H NMR spectra for 1[PF 6 ] and 2[PF 6 ] are a consequence of restricted rotation associated with the three Rh-C NHC bonds. Line shape analyses from the NMR studies on 1[PF 6 ], 1[BAr 4 F ], and 2[PF 6 ] (BAr 4 F) B(3,5-C 6 H 3 (CF 3) 2) 4) afford activation barriers for the two trans-positioned Rh-C NHC bonds of 35, 38, and 40 kJ mol-1 , respectively. Pulsed-gradient spin-echo (PGSE) NMR measurements show that there is only a relatively small amount of ion pairing for these salts in dichloromethane solution. 1 H-19 F HOESY data help to place the anions relative to the cations. Preliminary mechanistic studies on the formation of 1 and 2 suggest a role for neutral dinuclear precursors, as revealed by the reaction of (PPh 3) 2 Rh(µ-CO) 2 Rh(I i Pr 2 Me 2) 2 with ICy, which affords the structurally characterized mixed NHC complex [Rh(I i Pr 2 Me 2) 2 (ICy)(CO)][PF 6 ] (3[PF 6 ]).
Inorganic Chemistry, 2008
Arene ruthenium(II) complexes containing bis(pyrazolyl)methane ligands have been prepared by reacting the ligands L′ (L′ in general; specifically L 1 ) H 2 C(pz) 2 , L 2 ) H 2 C(pz Me2 ) 2 , L 3 ) H 2 C(pz 4Me ) 2 , L 4 ) Me 2 C(pz) 2 and L 5 ) Et 2 C(pz) 2 where pz ) pyrazole) with [(arene)RuCl(µ-Cl)] 2 dimers (arene ) p-cymene or benzene). When the reaction was carried out in methanol solution, complexes of the type [(arene)Ru(L′)Cl]Cl were obtained. When L 1 , L 2 , L 3 , and L 5 ligands reacted with excess [(arene)RuCl(µ-Cl)] 2 , [(arene)Ru(L′)Cl][(arene)RuCl 3 ] species have been obtained, whereas by using the L 4 ligand under the same reaction conditions the unexpected [(p-cymene)Ru(pzH) 2 Cl]Cl complex was recovered. The reaction of 1 equiv of [(p-cymene)Ru(L′)Cl]Cl and of [(p-cymene)Ru(pzH) 2 Cl]Cl with 1 equiv of AgX (X ) O 3 SCF 3 or BF 4 ) in methanol afforded the complexes [(p-cymene)Ru(L′)Cl](O 3 SCF 3 ) (L′ ) L 1 or L 2 ) and [(p-cymene)Ru(pzH) 2 Cl]BF 4 , respectively. [(p-cymene)Ru(L 1 )(H 2 O)][PF 6 ] 2 formed when [(p-cymene)Ru(L 1 )Cl]Cl reacts with an excess of AgPF 6 . The solid-state structures of the three complexes, [(p-cymene)Ru{H 2 C(pz) 2 }Cl]Cl, [(p-cymene)Ru{H 2 Cpz 4Me ) 2 }Cl]Cl, and [(pcymene)Ru{H 2 C(pz) 2 }Cl](O 3 SCF 3 ), were determined by X-ray crystallographic studies. The interionic structure of [(pcymene)Ru(L 1 )Cl](O 3 SCF 3 ) and [(p-cymene)Ru(L′)Cl][(p-cymene)RuCl 3 ] (L′ ) L 1 or L 2 ) was investigated through an integrated experimental approach based on NOE and pulsed field gradient spin-echo (PGSE) NMR experiments in CD 2 Cl 2 as a function of the concentration. PGSE NMR measurements indicate the predominance of ion pairs in solution. NOE measurements suggest that (O 3 SCF 3 )approaches the cation orienting itself toward the CH 2 moiety of the L 1 (H 2 C(pz) 2 ) ligand as found in the solid state. Selected Ru species have been preliminarily investigated as catalysts toward styrene oxidation by dihydrogen peroxide, [(p-cymene)Ru(L 1 )(H 2 O)][PF 6 ] 2 being the most active species.
Journal of the American Chemical Society, 1999
A series of homoleptic cations of Rh(I,II), Rh(II), and Rh(III) have been synthesized and characterized in the solid-state and in solution. Three new dinuclear compounds of dirhodium(II,II) were prepared by treatment of Rh 2 (O 2 CCH 3 ) 4 (L) 2 with Et 3 OBF 4 or Me 3 Si(CF 3 SO 3 ) in acetonitrile or propionitrile. The cations in [Rh 2 II,II -(MeCN) 10 ][BF 4 ] 4 (1), [Rh 2 II,II (MeCN) 10 ][SO 3 CF 3 ] 4 (2), and [Rh 2 II,II (EtCN) 10 ][BF 4 ] 4 (3) contain eight equatorial RCN groups oriented in an approximately square planar arrangement around the two Rh atoms and two axial RCN molecules. The redox properties of 1-3 were investigated by cyclic voltammetry, which revealed the presence of one or two irreversible reduction(s) but no oxidations. Although there was no electrochemical evidence for an accessible oxidation, it was found that treatment of [Rh 2 II,II (MeCN) 10 ][BF 4 ] 4 with NOBF 4 occurs to yield another member of the homoleptic acetonitrile family, namely, the octahedral d 6 cation [Rh III -(MeCN) 6 ][BF 4 ] 3 , (4). The corresponding one-electron reduction product was isolated by a slow galvanostatic reduction of [Rh 2 II,II (MeCN) 10 ][BF 4 ] 4 (1) in MeCN at a Pt electrode. The crystals harvested from the cathode were found to be the unprecedented mixed-valence 1-D chain compound [Rh I,II (MeCN) 4 (BF 4 ) 1.5 ] x (5), which result from a radical polymerization of the unstable Rh 2 I,II dinuclear cation. In an effort to access the final member of this series, namely, the homoleptic Rh I species, the dicarbonyl compound [Rh I (CO) 2 (MeCN) 2 ]-[BF 4 ] (6) was prepared, but all thermal and photochemical attempts to remove the CO ligands led to the conclusion that only one CO is labile. The mixed-ligand, square planar cation [Rh I (CO) 2 (MeCN) 2 ] + was found to form a 1-D stack in the solid state, unlike previously reported salts with bulky counterions. For all of the compounds under investigation, infrared spectroscopy and X-ray studies were performed. The mixed-valence product was also characterized by EPR spectroscopy and SQUID magnetometry.
Inorganica Chimica Acta, 1997
The reaction of Rua(OaCCH3)4CI with water in the presence of AgaSO 4 and NH~PF 6 leads to the formation of [Ru 2-(OzCCH3)4(HaO)al(PF~) (1). The subsequent reaction of complex ] with dimethylformamida (DMF) and dimethylanlfoxule (DMSO) results in the formation of [Ru2(OaCCH3)4(DMF)2](PF6) (2); [Rna(OaCCH314(DMF/a](PF6).DMF (aa) aral [Rua(OaCCH3)~-(DMSO)2] (PF6) (3). All complexes were characterized using single crystal X-ray crystallography, IR and UV-Vis spectmscogff, cyclic vultammetry and magnetic susceptibility. The crystallographic data for [Rua(OaCCH3)4(HaO)a] (PF6). 3H20 (la) are as fullow~ nudeclinic, space group C2/e with unit cell dimensions a = 19.552(2). b= 12-853(2/. c= 8.487(2) A. fl= 93.09(2) °, V= 2129.6(61 A3,Z=4. The structure was refined to R = 0.0244 (R~ ~ 0.0266) with 1165 reflections having I> 3o'(1). The Ru-Rn distance is 2,2648(91 A; RwO distances are 2.023(4/, 2,039(3), 2.018(4) and 2.026 A; Ru-O(axial) =2.279(4) A. The relevant data for 2 a~: mthodmmbic, space group P212121 with unit cell dimensions a = 11.704(2), b~ 28.452( 101, c-8.415( 31 A, V-2802(2) A 3, Z-4. The stn.'ctme was reraned to R=0.0597 (wR2 ~0.1520) with 909 reflections having 1>2o-(/). The Ru-Ru distance is 2.262(3) A; Ru-O distances ate 1.999(14), 2.003(13), 2.004(13) and 2.009(13) ~; the Ru~(axial) distances are both 2.22(2) A. The pertinent crystal daul for 2a are: mo~x:tinic, space group P21/c with unit cell dimensions a=8.382(4), b= 11.918(3), c~30.715(5) A, fl=96.84(3) °, V=3046(11 ~3 Z~4. Tic: structure was refined to R=0.0558 (wR2=0.1388) with 1317 reflections having 1>2o'(/). The Ru-Ru distance is 2.265(2) A.; Ru-O distances are 2,021(13), 2.052(13). 2.009(13) and 2.023(14) A; the Ru--O(axial) distances are both 2.229(t4) A. The data for 3 are: tric~idic° space gr~p P~ with ~ni~ ea~ ~ dim~nsi~ns a ~ ~ ~ . 45 ( ~ ) ~ b~ ~ 4. ~ ~3 ( 4 ) ' c ~ 8.3~3 ( 3 ) .A~ a ~ 9~.46( 2 )~ ~ ~ ~ ~.~ 5 ( 41° ~/~ 78.93( 4 ) % V= 1232(1) A 3, Z=2. The structure was refined to R=0.0301 (R~ ~0.0382) with 2758 reflections having 1> 3o'(/}. The Ru--Ru bond distances are 2.274( 1 ) and 2.268( I ) A; Ru-O distances range from 2.017(51 to 2.035(51 ~; the Ru-O(asial) d~tances ate 2.240(5) and 2.243(51 A. Increasing the donor number of the axial ligand manifests only very small changes in Ru-Ru bond length, reducfico and ~'~ (Rua) ~ 7r( RuO, Ru2) transition energy and no changes in/~nimplying only minor perturbation of b'* and ~* offal energies. five) and labile trans axial sites for subsequent linenc chain construction.
Organometallics, 1986
Reaction of H2C(S02CF3)2 with (Ph3P),RuH2 in neat arene solvents produces (a-arene)RuH(PPh3).zf-HC(SO2CF&-. The lH NMR spectra of these compounds indicate that substituents on the arene ring stabilize one of several ring rotational conformations. Molecular orbital calculations at the extended Huckel level were utilized to explore the structural distortion of the RuH(PPh&+ units in these compounds as well as the dynamics of rotation about the arene-Ru axis. Computations on (arene)RuH(PH&+ (arene = benzene, aniline, phenylborane) each showed similar distortions in the tripod portion of the molecule which can be traced to more efficient donation of electron density from the hydride to the metal compared to the phosphine ligands. The structure for each of these model compounds was optimized, and barriers to rotation about the arene-Ru bond were computed. Crystal structure determinations on (r-PhCHJ-
Organometallics, 2006
This study reports the isolation and the structural (X-ray), UV-vis, and NMR characterization of a series of electron-rich Ru(II) acetylide complexes of the formula (η 2 -dppe)(η 5 -C 5 Me 5 )Ru(CtC)-1,4-(C 6 H 4 )X (1a-f; X ) NO 2 , CN, F, H, OMe, NH 2 ) and (η 2 -dppe)(η 5 -C 5 Me 5 )Ru(CtC)-1,3-(C 6 H 4 )F (1c-m), as well as the spectroscopic (near-IR and ESR) in situ characterization of the corresponding elusive Ru(III) radical cations. The spectroscopic data are discussed in connection with DFT computations, and a consistent picture of the electronic structure of these Ru(II) and Ru(III) acetylide complexes is proposed. Notably, the strong reactivity of the Ru(III) radicals evidenced in this contribution constitutes a major difference with the relative stability of the known iron analogues. * To whom correspondence should be addressed. Fax: (33) 2 23 23 56 37 (F.P.); (61) 8 8303 4358 (M.I.B.). (1) See for instance: (a) Cifuentes, M. P.; Humphrey, M. G.; Morall, J. P.; Samoc, M.; Paul, F.; Roisnel, T.; Lapinte, C. Organometallics 2005, 24, 4280-4288. (b) Blum, A. S.; Ren, T.; Parish, D. A.; Trammell, S. A.; Moore, M. H.; Kushmerick, J. G.; Xu, G.-L.; Deschamps, J. R.; Polack, S. K.; Shashidar, R. Perruchon, J.; Blanchard, P.; Roncali, J.; Gohlen, S.; Allain, M.; Migalska-Zalas, A.; Kityk, I. V.; Sahraoui, B. Organometallics 2005, 24, 687-695. (d) Qi, H.; Sharma, S.; Li, Z.; Snider, G. L.; Orlov, A. O.; Lent, S. S.; Fehlner, T. P. Fox, T.; Schmalle, H. W.; Berke, H. Organometallics 2005, 24, 2834-2847. (b) Venkatesan, K.; Blacque, O.; Fox, T.; Alfonso, M.; Schmalle, H. W.; Berke, H. Venkatesan, K.; Blacque, O.; Alfonso, M.; Schmalle, H.; Berke, H. Chem. Eur. J. 2003, 9, 6192-6209. (d) Venkatesan, K.; Fernandez, F. J.; Blacque, O.; Fox, T.; Alfonso, M.; Schmalle, H. W.; Berke, H.
Eur. J. Inorg. Chem. 2001, 633
A novel one-pot synthesis of rhenium-based triangular prismatic cages has been accomplished in excellent yields by a self-assembly strategy. Reaction of Re 2 (CO) 10 with 2,4,6-tri-4-pyridyl-1,3,5-triazine (tpt) in the presence of an aliphatic alcohol (1-butanol, 1-octanol or 1-dodecanol) afforded molecular prisms, [{(CO) 3 Re(µ 2 -OR) 2 Re(CO) 3 } 3 (µ 3 -tpt) 2 ] (1, R = C 4 H 9 ; 2, R = C 8 H 17 ; 3, R = C 12 H 25 ) by solvothermal methods. Fine tuning of the solubility is achieved by tailoring the [a]
Preparation and structure of Ru3 (CO) 7 (. mu. 3-. eta. 2-C6H4)(. mu.-PPhFc) 2
…, 1988
methyl-3-pentanone, 565-80-0; 2-methyl-3-isopropyl-6-hepten-3-01, Supplementary Material Available: Listings of atomic 38443-89-9; 2,3-dimethyl-3-butene, 563-78-0; 2,3-dimethyl-2-coordinates for hydrogen atoms with isotropic temperature factors, butene, 563-79-1; 2,5,6-trimethyl-3-isopropyl-6-hepten-3-01-anisotropic thermal parameters for non-hydrogen atoms, and bond 4,4,7,7-d4, 115982-94-0; 2,5,6-trimethy1-3-isopropyl-6-hepten-3-01, distances and angles including hydrogen atoms (3 pages); a listing 115982-95-1; 2,4,5-trimethyl-5-hexen-2-ol-3,3,6,6-d4, 115982-96-2; of observed and calculated structure factors (48 pages). Ordering 2,4,5-trimethyl-5-hexen-2-01, 115982-97-3; acetone, 67-64-1. information is given on any current masthead page.
Inorganica Chimica Acta, 1995
Reaction of RuCI(r~-C5Hs)(pToI-DAB) with AgOTf (OTf=CF3SO3) in CH2C12 or THF and subsequent addition of L' (L' =ethene (a), dimethyl fumarate (b), fumaronitrile (c) or CO (d)) led to the ionic complexes [Ru(~-C5H5) (pTol-DAB) (L') ] [OTf] (2a, 2b and 2d) and [Ru(rf-C5H5) (pTol-DAB) (fumaronitrile-N) ] [OTf] (5e). With the use of resonance Raman spectroscopy, the intense absorption bands of the complexes have been assigned to MLCT transitions to the iPr-DAB ligand. The X-ray structure determination of [Ru(rf-C5H5 ) (pTol-DAB) (rf-ethene) ] [ CF3SO3 ] ( 2a ) has been carried out. Crystal data for 2a: monoclinic, space group P2 t / n with a = 10.840 ( 1 ), b = 16.639 ( 1 ), c = 14.463 (2) A,/3 = 109.6 ( 1 )°, V = 2465.6 (5) A 3, Z = 4. Complex 2a has a piano stool structure, with the Cp ring ~-bonded, the pToi-DAB ligand crN, ~rN' bonded (Ru-N distances 2.052(4) and 2.055(4) A), and the ethene ~2-bonded to the ruthenium center (Ru-C distances 2.217 (9) and 2.206 (8) .~). The C fC bond of the ethene is almost coplanar with the plane of the C p ring, and the angle between the plane of the Cp ring and the double bond of the ethene is 1.8 (0.2)°. The reaction of RuC1 (rf-CsHs)(PPh3)2 with AgOTf and ligands L' = a and d led to [Ru ( Tf-CsH 5) (PPh3) 2 (L') ] [ OTf] (3a) and (3d), respectively. By variable temperature NMR spectroscopy the rotational barrier of ethene (a), dimethyl fumarate (b) and fumaronitrile (c) in complexes [Ru(~-C~H5) (I-a) (~2-alkene) ] [OTf] with L 2 = iPr-DAB (la, lb, lc), pTol-DAB (2a, 2b) and L = PPh3 (3a) was determined. For la, lb and 2b the barrier is 41.5 + 0.5, 62 + 1 and 59 + 1 kJ mgl-1, respectively. The intermediate exchange could not be reached for lc, and the AG* was estimated to be at least 61 kJ mol-1. For 2a and 3a the slow exchange could not be reached. The rotational barrier for 2a was estimated to be 40 kJ mol-~. The rotational barrier for methyl propiolate (HC-CC(O)OCH3) (k) in complex [Ru(r~-CsHs) (iPr-DAB) ('r/2-HC~-CC(O)OCH3) ] [OTf] (lk) is 45.3 + 0.2 kJ tool-1.