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BIS(1 5-CYCLOOCTADIENE)RHODIUM(I) - CAS 207124-65-0

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Category
Main Product
Product Name
BIS(1 5-CYCLOOCTADIENE)RHODIUM(I)
Catalog Number
207124-65-0
Synonyms
(1Z,5Z)-cycloocta-1,5-diene;rhodium;tetrafluoroborate;hydrate;207124-65-0;Bis(1,5-cyclooctadiene)rhodium(I)tetrafluoroboratehydrate
CAS Number
207124-65-0
Molecular Weight
406.07
Molecular Formula
C16H24BF4Rh
COA
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MSDS
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Canonical SMILES
[B-](F)(F)(F)F.C1CC=CCCC=C1.C1CC=CCCC=C1.O.[Rh]
InChI
InChI=1S/2C8H12.BF4.H2O.Rh/c2*1-2-4-6-8-7-5-3-1;2-1(3,4)5;;/h2*1-2,7-8H,3-6H2;;1H2;/q;;-1;;/b2*2-1-,8-7-;;;
InChIKey
RVVSQTPAHKVLPL-DIURZKMRSA-N
Structure
CAS 207124-65-0 BIS(1 5-CYCLOOCTADIENE)RHODIUM(I)
Specification
Purity
95%
Melting Point
165ºC (dec.)(lit.)
Appearance
Orange to red-brown powder, crystals and/or chunks
Reference Reading
1.Synthesis of new late transition metal P,P-, P,N-, and P,O- complexes using phosphonium dimers as convenient ligand precursors.
Park K1, Lagaditis PO, Lough AJ, Morris RH. Inorg Chem. 2013 May 6;52(9):5448-56. doi: 10.1021/ic4003753. Epub 2013 Apr 9.
The phosphonium dimer [-Cy2PCH(OH)CH2-]2(X)2, X = Cl(-), Br(-) was used to synthesize and characterize a variety of late transition metal complexes containing chelating phosphino-enolate (PCy2CH═CHO(-)), imine (PCy2CH2CH═NR, R = Ph, (S)-CHMePh), and oxime (PCy2CH2CH═NOH) ligands. The phosphonium dimer, when deprotected with base, generates the phosphine aldehyde PCy2CH2CHO in situ, which, in the presence of [M(COD)Cl]2, M = Rh, Ir, and a PF6(-) salt, or [Ni(H2O)6][BF4]2, facilitates a condensation reaction with an amine or hydroxylamine to form phosphino-imine or phosphino-oxime metal complexes [M(COD)(P-N)][PF6] or [Ni(P-N)2][X]2, X = ClO4(-), BF4(-), respectively. In the absence of an amine, phosphino-enolate containing complexes are formed. A neutral Ni(II) complex Ni(PCy2CH═CHO)2 with trans-bis(phosphino-enolate) ligands which resemble ligands used on nickel for olefin oligomerization, as well as neutral Rh(I) and Ir(I) 1,5-cyclooctadiene complexes M(COD)(PCy2CH═CHO) are characterized.
2.Halogen oxidation and halogen photoelimination chemistry of a platinum-rhodium heterobimetallic core.
Cook TR1, McCarthy BD, Lutterman DA, Nocera DG. Inorg Chem. 2012 May 7;51(9):5152-63. doi: 10.1021/ic300004x. Epub 2012 Apr 4.
The heterobimetallic complexes, PtRh(tfepma)(2)(CN(t)Bu)X(3) (X = Cl, Br), are assembled by the treatment of Pt(cod)X(2) (cod =1,5-cyclooctadiene) with {Rh(cod)X}(2), in the presence of tert-butylisonitrile (CN(t)Bu) and tfepma (tfepma = bis(trifluoroethoxyl)phosphinomethylamine). The neutral complexes contain Pt-Rh single bonds with metal-metal separations of 2.6360(3) and 2.6503(7) Å between the square planar Pt and octahedral Rh centers for the Cl and Br complexes, respectively. Oxidation of the XPt(I)Rh(II)X(2) cores with suitable halide sources (PhICl(2) or Br(2)) furnishes PtRh(tfepma)(2)(CN(t)Bu)X(5), which preserves a Pt-Rh bond. For the chloride system, the initial oxidation product orients the platinum-bound chlorides in a meridional geometry, which slowly transforms to a facial arrangement in pentane solution as verified by X-ray crystal analysis. Irradiation of the mer- or fac-Cl(3)Pt(III)Rh(II)Cl(2) isomers with visible light in the presence of olefin promotes the photoelimination of halogen and regeneration of the reduced ClPt(I)Rh(II)Cl(2) core.
3.Synthesis and characterisation of group nine transition metal complexes containing new mesityl and naphthyl based azaindole scorpionate ligands.
Owen GR1, Tsoureas N, Hope RF, Kuo YY, Haddow MF. Dalton Trans. 2011 Jun 14;40(22):5906-15. doi: 10.1039/c0dt01576h. Epub 2011 Apr 28.
Two novel boron-based flexible scorpionate ligands based on 7-azaindole, Li[HB(azaindolyl)(2)(1-naphthyl)] and Li[HB(azaindolyl)(2)(mesityl)] {Li[(Naphth)Bai] and Li[(Mes)Bai] respectively}, have been prepared (mesityl = 2,4,6-trimethylphenyl). These salts have been isolated in two forms, either as dimeric structures which contain bridging hydride interactions with the lithium centres or as crystalline material containing mono nuclear bis-acetonitrile solvates. The newly formed ligands have been utilised to prepare a range of group nine transition metal complexes with the general formula [M(COD){κ(3)-NNH-HB (azaindolyl)(2)(Ar)}] (where M = rhodium, iridium; Ar = 1-naphthyl, mesityl; COD = 1,5-cyclooctadiene) and [Rh(NBD){κ(3)-NNH-HB (azaindolyl)(2)(Ar)}] (where NBD = 2,5-norbornadiene; Ar = 1-naphthyl, mesityl). These new complexes have been compared to the previously reported compounds which contain the related scorpionate ligands Li[HB(azaindolyl)(2)(phenyl)] and K[HB(azaindolyl)(3)] {Li[(Ph)Bai] and K[Tai] respectively}.
4.Rhodium and iridium complexes of a new ferrocene-derived chelating bis(NHC) ligand.
Panov DM1, Petrovskii PV, Ezernitskaya MG, Smol'yakov AF, Dolgushin FM, Koridze AA. Dalton Trans. 2012 Aug 28;41(32):9667-71. doi: 10.1039/c2dt30898c. Epub 2012 Jul 9.
Rhodium and iridium complexes of a new ferrocene-derived bis(N-heterocyclic carbene) ligand, [M(cod){1,2-(MeNCHCHNCCH(2))(2)C(5)H(3)}Fe(C(5)H(5))]BF(4) (M = Rh, 8a; M = Ir, 8b; cod = 1,5-cyclooctadiene), were synthesized from the corresponding bis(imidazolium) salt 6. The molecular structure of 8a was determined by single-crystal X-ray diffraction. Complexes 8a and 8b smoothly react with CO with displacement of the chelating cod ligand to give the corresponding dicarbonyl derivatives 9a and 9b.
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