RATES AND ACTIVATION PARAMETERS FOR SOLVENT EXCHANGE WITH (1+) (M = RhIII OR IrIII, R = CYCLOHEXYL OR PHENYL) CATIONS

DOI: 10.1039/DT9810001481

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1481 - 1485 (1981)

Update date:2022-08-05

Topics:

Authors:

Howarth, W. Oliver

McAteer, Colin H.

Moore, Peter

Morris, George E.

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1039/DT9810001481

Using ₁H n.m.r. line-broadening and, where possible, stopped-flow Fourier-transform n.m.r., rates and activation parameters have been determined for solvent exchange with complexes of the type (1+) (M = Rh_III or Ir_III; R = phenyl, solvent = MeCN or Me2CO; R = cyclohexyl, solvent = MeCN) in <₂H²>-dichloromethane solution.In all cases the co-ordinated solvent molecules are in trans positions with respect to the hydride ligands, and at 298 K the various complexes have rate constans for solvent exchange (k¹) which differ almost by a factor of 10₇; k¹(Rh) > k¹(Ir) because for analogous species ΔH<*>(Rh) < ΔH<*>(Ir), and the acetone solvates are much more labile than the acetonitrile complexes because of lower ΔH<*> values.Values of ΔS<*> are significantly positive (8-32 J K_-1mol_-1 when M = Rh_III, 25-30 J K_-1mol_-1 when M= Ir_III) in line with a dissociative, D mechanism.Hydrogen-1 n.m.r. spectra of (1+) and (1+) ions (L = MeOH, MeCN, pyridine, styrene, or cyclo-octene) are reported and compared.

Full text of DOI:10.1039/DT9810001481

View Article Online / Journal Homepage / Table of Contents for this issue

View Article Online

Products guided by the article

Product name:cis,trans,cis-[Rh(H)2(PPh₃)2(acetone)2][PF₆]

Cas No:82404-88-4

R&D Labs maybe for 82404-88-4

Ningbo Huajia Chemicals

Contact:+86-574-87065746

Address:10th Floor, No.787 Baizhang East Road,
LinHai Cina Chemical Co., LTD.

Contact:0576-85580989

Address:Pharma-chem zone,Duqiao,Linhai,Zhejiang,China
Beijing Wisdom Chemicals Co., Ltd.

Contact:+86-10-52350335

Address:F2, BLDG 19, Liando Valley U, Majuqiao, Tongzhou District, Beijing, China
Hefei Highzone Fine Chemical S&T CO.,LTD

Contact:86-0551-63663560

Address:room 1801 NO. 24 Shuguang RD.
Shenzhen Sunrising Industry Co., ltd.

Contact:+86 755 86571158 / 86571159 / 86571160

Address:2108 ZHENYE INT. BUSINESS CENTER,NO.3101-90 QIANHAI RD, NANSHAN,SHENZHEN, CHINA

Relevant to this article

Electrochemically induced one pot synthesis of 1,4-dihydropyrano[2,3-c]-pyrazole-5-carbonitrile derivatives via a four component-tandem strategy

Doi:10.1016/j.tetlet.2017.01.049
(2017)
Novel Synthesis of Five- and Six-Membered Spiro γ-Lactones in Rigid Bicyclic Systems

Doi:10.1021/jo00141a028
(1982)
Direct transformation of silyl enol ethers into functionalized allenes

Doi:10.1002/1521-3765(20010202)7:3<573::AID-CHEM573>3.0.CO;2-I
(2001)
Fluorinated tricyclic neuroleptics with prolonged action: 8-alkyl derivatives of 3-fluoro-10-piperazino-10,11-dihydrodibenzo[b,f]thiepins

Doi:10.1135/cccc19842638
(1984)
DEPENDENCE OF ANTIINFLAMMATORY ACTIVITY ON THE PHYSICOCHEMICAL PARAMETERS OF SUBSTITUENTS IN A SERIES OF ORGANOSELENIUM COMPOUNDS

Doi:10.1007/BF00773817
(1984)
Doi:10.1021/ja01315a043
(1935)

Article Doi