Nova Complexes or Rhodium(I) Containing Bridging SO2 Ligands

Cowie, Martin; Dwight, Stephen K.; Sanger, Alan R.

doi:10.1016/s0020-1693(00)94940-5

Cited by 24 publications

(11 citation statements)

References 15 publications

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“…The methylene groups are cis, i.e., they are folded in the same direction, toward the Cl ligapd. In DPM complexes this is typical, 3,5,6,9,40 namely, that the methylene group bends toward the larger ligand or the more sterically encumbered position, thereby minimizing the repulsive contacts involving the more bulky phenyl groups. One exception to this is Fe2(DPM)(CO)741 in which the methylene ligand is folded away from the bridging carbonyl ligand and toward the open site opposite this ligand.…”

Section: Discussionmentioning

confidence: 99%

Structure of [Rh2(CO)2(.mu.-CO)(.mu.-Cl)((C6H5)2PCH2P(C6H5)2)2][B(C6H5)4]: an "A-frame" complex having a carbonyl ligand coordinated in the proposed active site

Cowie¹

1979

Inorg. Chem.

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Martin CowieBoth compounds show deviation from tetrahedral angles about the amine nitrogens (N(3) and N(4)) with the external C-N-C angles opening to nearly 120°to facilitate the tetradentate coordination. In both cases the M-N-0 angles are slightly larger («122°) than the "ideal" 120°s p2 angle which tends to slightly lengthen the hydrogen bond. Other bond angles in the two cases are also very similar. The bond distances in the two compounds are generally in agreement except for the oxime N-0 distances (average 1.383 Á in this complex and average 1.356 Á in the Ni complex) and the adjacent N(oxime)-C distances (average 1.271 Á in this complex and average 1.288 A in the nickel complex). The apparent shift in the multiple bonding from the N-0 toward C-N bond in this complex may be a result of the longer hydrogen bond (O-O, 2.698 Á) in this complex compared with the case of the nickel complex (2.474 A). The longer N-0 distance (1.398 A) involves the oxygen to which the hydrogen atom is bonded in a nearly covalent fashion (O-H, 0.75 A from difference Fourier position). The other O-H distance is 1.95 A. The hydrogen bond in this complex is much longer than that in any other -amine oxime complex we have studied. This may be partially due to the steric requirements of the ligand with the larger Cu(II) metal but is probably also partially a result of the dimerization which involves coordination of one of the hydrogen bond oxime oxygens with the copper. Attempts are under way to obtain single crystals with some other better coordinating anion replacing the perchlorate ion in hopes of obtaining a monomer.Acknowledgment. Financial support of the National Science Foundation (Grant CHE77-08325) is gratefully acknowledged.Registry No. [Cu(EnAO-H)]2(C104)2, 68492-44-4. Supplementary Material Available: Hydrogen atom positional parameters and a listing of structure factor amplitudes (14 pages). Ordering information is given on any current masthead page.

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Section: Discussionmentioning

confidence: 99%

Structure of [Rh2(CO)2(.mu.-CO)(.mu.-Cl)((C6H5)2PCH2P(C6H5)2)2][B(C6H5)4]: an "A-frame" complex having a carbonyl ligand coordinated in the proposed active site

Cowie¹

1979

Inorg. Chem.

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“…Similar bridged complexes are obtained by reaction of SO, or other two-electron donor ligands (2,3,(12)(13)(14)(15)(16), but it should be noted that attack by SO, occurs directly at the bridging site (9). Neutral dicarbonyl complexes have structure 5, and tetracarbonyl complexes have structure 3 (15a).…”

Section: Discussionmentioning

confidence: 67%

“…The synthesis and structure of related complexes of rhodium or iridium has since received much attention (2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16). For complexes of rhodium(I), several instances of co-ordination of two-electron donor ligands (L; e.g.…”

Section: Introductionmentioning

confidence: 99%

“…For complexes of rhodium(I), several instances of co-ordination of two-electron donor ligands (L; e.g. CO, SO,) at the site bridging the metal centers (2) have been reported (2,3,6,9,(12)(13)(14)(15)(16). The complex cation, [Rh,(y-Cl)(CO),-(dpm),lf, forms a 1: 1 labile, symmetrical (ir, 3'P nmr) complex with diphenylacetylene (6) ,2 and similar neutral complexes have also recently been described (11).…”

Section: Introductionmentioning

confidence: 99%

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Correlation of the hydrogénation catalytic activity of dinuclear complexes of rhodium(I) with the formation of carbonyl-bridged complexes

Sanger¹

1982

Can. J. Chem.

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Methanolic solutions of the dinuclear cationic complexes of rhodium(I), [Rh2(μ-X)(CO)2(Ph2ECH2EPh2)2]+ (X = Cl, Br; E = P, As) and iridium(I), [Ir2Cl(CO)3(Ph2PCH2PPh2)2], are each active catalysts for the hydrogenation of alkynes to alkenes, and alkenes to alkanes. Neutral complexes with pseudohalide ligands have also been investigated but only the cyano-complex [Rh2(CN)2(CO)2(Ph2PCH2PPh2)2], and the arsine analog, are of significant catalytic activity. Only those complexes which reversibly form bridged complexes with ligands such as CO are also catalytically active.Similar complexes with dithioether ligands are not efficient catalysts under the conditions tested.

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“…of 66.51(4)' observed in the Rh-Rh bonded carbonyl adduct 2. In addition, the absence of a formal metal-metal bond is required to explain the observed diamagnetism and to give each rhodium atom a 16-electron configuration.The Rh-Cl distances of 2.406 (2) and 2.380(2) A are in the range typically observed in other chloro-bridged dimer systems (ca.…”

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confidence: 95%

Structure of [Rh2(CO)2(.mu.-Cl)((C6H5)2PCH2P(C6H5)2)2][BF4]. A binuclear "A-frame" complex showing the open "active" site

Cowie¹,

Dwight²

1979

Inorg. Chem.

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The structure of the complex [Rh2(C0)2(pC1)((C6H5)2PCHZP(C6H5)2)2] [BF,] has been determined by X-ray crystallography, verifying that it is an "A-frame" type species. The structural parameters are similar in most aspects to those of the closely related species [Rh2(CO)2(p-S)((C6H5)2PCH2P(C6H5)2)2], with the significant difference that the "active" site, bridging the two metal centers, is more open to attack by small molecules in the present complex. The title complex crystallizes in the space group C,'-Pi from an acetone solution containing as the only anions PF6-and B(C6HS)c. Evidence suggests that the BFanion results from the leaching of boron from the glass by HF. The reduced unit cell has dimensions n = 13.044 (1) A, b = 14.962 (2) A, c = 12.800 (2) A, a = 96.20 (l)', / 3 = 92.56 (l)O, and y = 86.42 (1)' with 2 = 2. On the basis of 5729 unique, observed reflections the structure was refined by full-matrix, least-squares techni ues to agreement (7) and 1.807 (7) A, Rh-C1 = 2.380 (2) and 2.406 (2) A, C-0 = 1.184 (8) and 1.202 (8) A, Rh-Rh = 3.1520 (8) A, C-Rh-C1 = 170.9 (2) and 172.6 (3)O, and Rh-C1-Rh = 82.38 (5)'. indices of R = 0.046 and R, = 0.064. Some relevant metrical parameters are Rh-P(av) = 2.321 (2) w , Rh-C = 1.794 0020-1669/79/1318-2700$01 .OO/O 1 1 reacts reversibly with C02,s and S024,5,8 and undergoes facile reactions with several other small molecules, including NO, N,Ph+, CS,,9 and TCNE.'O The reactions with CO and SO2 contrast the two possible modes of attack of small molecules a X c , Y,, and Z , are the fractional coordinates of the centroid of the rigid group.The rigid group orientation angles 6 , E , and 17 (radians) are the angles by which the rigid body is rotated with respect to a set of axes X, Y , and Z. The origin is the center of the ring; X is parallel to u * , Z is parallel to c, and Y is parallel to the line defined by the intersection of the plane containing a* and b* with the plane containing b and C.amplitudes of vibration of the individual nonhydrogen atoms, and a listing of observed and calculated structure factor amplitudes used in refinement are a~ai1able.l~ Preparation of [Rh2(CO),(p-CI)(DPM)2][BF4]. To a solution of 0.100 g (0.077 mmol) of [Rh,(CO),(p-Cl)(DPM),] [Rh(CO),ClJ in 10 mL of acetone was added 0.017 g (0.150 mmol) of NaBF4. Slow Reaction of [Rh2(p-OH)3($-C5Me5)2]Cl.4H20 in water with hydrogen (90 O C , 1 atm) gives the green tetranuclear dication [Rh4H4(C5Me5)4]2t, 2Y-(Y-= C1-, PF,-, or BF,; 2Y-= PtCl:-). The BF4salt was characterized by X-ray crystallography (tetragonal unit cell with a = 11.763 ( 5 ) 8, and c = 15.522 (6) A, space group la), the structure was solved by Patterson and Fourier techniques and gave a final R of 0.039. The dication contains four rhodium atoms, each bearing a f'-C5Me5ligand, arranged in a distorted tetrahedral manner (D,d symmetry) with two short (2.655 (1) A) and four long (2.829 (1) A) Rh-Rh bonds. The presence of four hydride ligands in the cation has been shown by N M R spectroscopy; they do not take part in any major fluxiona...

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Nova Complexes or Rhodium(I) Containing Bridging SO2 Ligands

Cited by 24 publications

References 15 publications

Structure of [Rh2(CO)2(.mu.-CO)(.mu.-Cl)((C6H5)2PCH2P(C6H5)2)2][B(C6H5)4]: an "A-frame" complex having a carbonyl ligand coordinated in the proposed active site

Structure of [Rh2(CO)2(.mu.-CO)(.mu.-Cl)((C6H5)2PCH2P(C6H5)2)2][B(C6H5)4]: an "A-frame" complex having a carbonyl ligand coordinated in the proposed active site

Correlation of the hydrogénation catalytic activity of dinuclear complexes of rhodium(I) with the formation of carbonyl-bridged complexes

Structure of [Rh2(CO)2(.mu.-Cl)((C6H5)2PCH2P(C6H5)2)2][BF4]. A binuclear "A-frame" complex showing the open "active" site

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