The Rh(III) methyl complexes Rh(mac)(Ch
3)L (mac = 1,2-bis(2- pyridinecarboxamido)benzene (bpb) or tetra(p-tolyl)porphyrin dianion (TTP), octaethylporphyrin dianion (OEP); L = unidentate ligand), [Rh(mac)(CH
3)]
2(μ-L') [L'= 4-cyanopyridine (4-CN-py) or 4,4'-bipyridine (4,4'-bipy)] have been synthesized and characterized. The structures of Rh(bpb)(CH
3) (4-[tert]Bu-py) (4-[tert]Bupy = 4-tert-butylpyridine), Rh(bpb)(CH
3) (PMe
2Ph), and [Rh(TTP)(CH
3)]
2(μ-4-CN-py) have been determined by X-ray crystallography. The Rh(TTP)R (R = 5-norbornene-2-methyl) have been synthesized and the structure have been established by X-ray crystallography. Ring opening metathesis polymerization of Rh(TTP)R with Ru(=CHPh)(PCy
3)
2Cl
2 leads to formation of a pentamer. Cis-Pt(L")
2(CH
3)
2 (L"
2 = (4-[tert]Bu-py)
2, (SEt
2)...[
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The Rh(III) methyl complexes Rh(mac)(Ch
3)L (mac = 1,2-bis(2- pyridinecarboxamido)benzene (bpb) or tetra(p-tolyl)porphyrin dianion (TTP), octaethylporphyrin dianion (OEP); L = unidentate ligand), [Rh(mac)(CH
3)]
2(μ-L') [L'= 4-cyanopyridine (4-CN-py) or 4,4'-bipyridine (4,4'-bipy)] have been synthesized and characterized. The structures of Rh(bpb)(CH
3) (4-[tert]Bu-py) (4-[tert]Bupy = 4-tert-butylpyridine), Rh(bpb)(CH
3) (PMe
2Ph), and [Rh(TTP)(CH
3)]
2(μ-4-CN-py) have been determined by X-ray crystallography. The Rh(TTP)R (R = 5-norbornene-2-methyl) have been synthesized and the structure have been established by X-ray crystallography. Ring opening metathesis polymerization of Rh(TTP)R with Ru(=CHPh)(PCy
3)
2Cl
2 leads to formation of a pentamer. Cis-Pt(L")
2(CH
3)
2 (L"
2 = (4-[tert]Bu-py)
2, (SEt
2)
2, COD, dppf and (PMe
3)
2 have been synthesized. The structure of Pt(dppf)(CH
3)
2 have been determined by X-ray crystallography.
The metal-carbon stretching frequencies for Rh(bpb)(CH
3)L, Rh(por) (CH
3)L, Ga(TTP)(CH
3) and In(TTP)(CH
3) have been determined by near infrared FT-Raman spectroscopy. It was found that the nature of L, the equatorial macrocyclic ligand, metal center and oxidation state of the metal center affect metal-carbon stretching frequency. For cis-Pt(L")
2(CH
3)
2 it was also found that the nature of L" has a pronounced influence on the Pt-C stretching frequency.
The heterobimetallic dinitrogen complexes [M(por)(N
2)Re(PMe
2Ph)
4Cl][OTf] and [M(por)(N
2)Re(Et
2dtc)(PMe
2Ph)
3 [OTf] (M = Fe, Ru(NO), Cr; por = OEP, TTP; OTf = triflate) have been synthesized and characterized by IR and UV/VIS spectroscopy. The structure of [Fe(por)(N
2) Re(PMe
2Ph)
4Cl] [OTf] has been established by X-ray crystallography. The Fe-N(N), Re-N, and N-N distances are 1.93(l), 1.832(l), and 1.17(1) Å, respectively; the Fe-N-N and Re-N-N angles being 170(1)° and 177(l)°, respectively. Heterobimetallic nitrido-bridged complexes, Ru(Et
2dtc)(PPh
3)
2(CO)[NOs(TolS
2)
2] (Et
2dtc = N,N-diethyldithiocarbamate; TolS
2 = 3,4-toluenedithiolate( 2-) and Ru(Et
2dtc)(PPh
3)
2(CO)[NOs(mnt)
2] (mnt = maleonitriledithiolate(2-)), have been synthesized and characterized by X-ray crystallography. A series of heterotrimetallic mnt complexes of the type [Ru(Et
2dtc)(PPh
3)
2(CO)]
2 [M(mnt)
2 (M = Ni, Pd, Pt, Cu) have been isolated and their formal potentials have been determined by cyclic voltammetry.
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