NDLI: Interaction of Triosmium Complexes with Hydrogen Chloride: A Model for Fine-Tuning Regioselective Protonation in Metal Clusters

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Journal of Cluster Science : Volume 9, Issue 3, September 1998

Journal of Cluster Science : Volume 9, Issue 2, June 1998

Journal of Cluster Science : Volume 9, Issue 1, March 1998

Journal of Cluster Science : Volume 8

Interaction of Triosmium Complexes with Hydrogen Chloride: A Model for Fine-Tuning Regioselective Protonation in Metal Clusters

Content Provider	Springer Nature Link
Author	Chung, Min Ling Lee, Fang Yuan Lin, Li Chun Su, Chi Jung Chen, Min Yen Wen, Yuh Sheng Gau, Han Mou Lu, Kuang Lieh
Copyright Year	1998
Abstract	The reaction of Os$_{3}$(CO)$_{10}$(CNR)(NCMe) (1) with HCl was studied and this system was found to be a good model for observing the fine-tuning of site-selective protonation in metal complexes. Three products including the protonated species [(ε-H)Os$_{3}$(CO)$_{10}$(CNR)(NCMe)]$^{+}$Cl$^{−}$ (2), the bridging aminocarbyne complex (µ-Cl)Os$_{3}$(CO)$_{10}$(µ$_{2}$-C = NHR) (3), and the hydrido derivative (ε-H)Os$_{3}$Cl(CO)$_{10}$(CNR) (4) were obtained for the reaction. The site of protonation, either on the Os center or on the nitrogen atom of coordinated isocyanide, was tuned in a sensitive manner by the nature of the coordinated isocyanides, the polarity of the solvents, and the strengths of the acids, leading to different product distributions. The more electron withdrawing isocyanides (CNCH$_{2}$Ph, CNPh) favor the formation of the aminocarbyne complex 3. In a nonpolar solvent like cyclohexane the reaction afforded 3 as the main product. Furthermore, complex 2 was converted to (ε-H)Os$_{3}$(CO)$_{10}$(ε$_{2}$-CONHR) (5) upon hydrolysis, in which the coordinated isocyanide was transformed to a carboxamido group. This was verified by obtaining the deuterated species (ε-H)Os$_{3}$(CO)$_{10}$(ε$_{2}$-CONDPr) when [(ε-H)Os$_{3}$(CO)$_{10}$(CNPr)(NCMe)]$^{+}$Cl$^{−}$ (2a) was treated with D$_{2}$O in THF. The molecular structures of (µ$_{2}$-Cl)Os$_{3}$(CO)$_{10}$(µ$_{2}$-C = NHCH$_{2}$Ph) (3b) and (ε-H)Os$_{3}$Cl(CO)$_{10}$(CNPr) (4a) were determined by X-ray diffraction analyses. Complex 3b contains both bridging chloride and bridging aminocarbyne groups, whereas 4a contains a terminal chloride, a terminal isocyanide and a bridging hydride.
Starting Page	445
Ending Page	463
Page Count	19
File Format	PDF
ISSN	10407278
Journal	Journal of Cluster Science
Volume Number	9
Issue Number	4
e-ISSN	15728862
Language	English
Publisher	Kluwer Academic Publishers-Plenum Publishers
Publisher Date	1998-01-01
Publisher Place	New York
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Inorganic Chemistry Physical Chemistry Catalysis
Content Type	Text
Resource Type	Article
Subject	Chemistry Biochemistry Condensed Matter Physics Materials Science

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Interaction of Triosmium Complexes with Hydrogen Chloride: A Model for Fine-Tuning Regioselective Protonation in Metal Clusters

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