Synthesis,structural characterisation and reactivity of molybdenum half-sandwich complexes containing keto- and amido-phosphines |
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| Institution: | 1. Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK;2. School of Chemistry, University of Bristol, Cantocks Close, Bristol BS8 1TS, UK;1. Department of Neurosurgery, Chonnam National University Medical School, Chonnam National University Hospital and Chonnam National University Hwasun Hospital, Gwangju, Republic of Korea;2. Department of Pediatrics, Chonnam National University Medical School, Chonnam National University Hospital and Chonnam National University Hwasun Hospital, Gwangju, Republic of Korea;3. Department of Radiology, Chonnam National University Medical School, Chonnam National University Hospital and Chonnam National University Hwasun Hospital, Gwangju, Republic of Korea;4. Department of Pathology, Chonnam National University Medical School, Chonnam National University Hospital and Chonnam National University Hwasun Hospital, Gwangju, Republic of Korea;1. Faculty of Chemistry, Bu-Ali Sina University, Hamedan 6517838695, Iran;2. Autophagy Research Center, Shiraz University of Medical Sciences, Shiraz, Iran;3. D-8 International University, Hamedan, Iran;1. Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266101, Shandong, PR China;2. Faculty of Engineering, Qingdao University of Science and Technology, Qingdao, 266042, PR China;1. Key Laboratory of Tropical Medicinal Resource Chemistry of Ministry of Education, College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou, 571158, Hainan, PR China;2. Key Laboratory of Water Pollution Treatment & Resource Reuse of Hainan Province, College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158, Hainan, PR China |
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| Abstract: | The keto-functionalised N-pyrrolyl phosphine ligand PPh2NC4H3{C(O)CH3-2} L1 reacts with MoCl(CO)3(η5-C5R5)] (R=H, Me) to give MoCl(CO)2(L1-κ1P)(η5-C5R5)] (R=H 1a; Me 1b). The phosphine ligands PPh2CH2C(O)Ph (L2) and PPh2CH2C(O)NPh2 (L3) react with MoCl(CO)3(η5-C5R5)] in an analogous manner to give the compounds MoCl(CO)2(L-κ1P)(η5-C5R5)] (L=L2, R=H 2a, Me 2b; L=L3, R=H 3a, Me 3b). Compounds 1–3 react with AgBF4 to give Mo(CO)2(L-κ2P,O)(η5-C5R5)]BF4 (L=L1, R=H 4a, Me 4b; L=L2, R=H 5a, Me 5b; L=L3, R=H 6a, Me 6b) following displacement of chloride. The X-ray crystal structure of 4a revealed a lengthening of both Mo–P and CO bonds on co-ordination of the keto group. The lability of the co-ordinated keto or amido group has been assessed by addition of a range of phosphines to compounds 4–6. Compound 4a reacts with PMe3, PMe2Ph and PMePh2 to give Mo(CO)2(L1-κ1P)(L)(η5-C5H5)]BF4 (L=PMe3 7a; PMe2Ph 7b; PMePh2 7c) but does not react with PPh3, 5a reacts with PMe2Ph, PMePh2 and PPh3 to give Mo(CO)2(L2-κ1P)(L)(η5-C5H5)]BF4 (L=PMe2Ph 8b; PMePh2 8c; PPh3 8d), and 6a reacts with PMe3, PMe2Ph, PMePh2 and PPh3 to give Mo(CO)2(L3-κ1P)(L)(η5-C5H5)]BF4 (L=PMe3 10a; PMe2Ph 10b; PMePh2 10c; PPh3 10d). No reaction was observed for the pentamethylcyclopentadienyl compounds 4b–6b with PMe3, PMe2Ph, PMePh2 or PPh3. These results are consistent with the displacement of the co-ordinated oxygen atom being influenced by the steric properties of the P,O-ligand, with PPh3 displacing the keto group from L2 but not from the bulkier L1. In the reaction of Mo(CO)2(L2-κ2P,O)(η5-C5H5)]BF4 (5a) with PMe3 the phosphine does not displace the keto group, instead it acts as a base, with the only observed molybdenum-containing product being the enolate compound Mo(CO)2{PPh2CHC(O)Ph-κ2P,O}(η5-C5H5)] 9. Compound 9 can also be formed from the reaction of 2a with BuLi or NEt3, and a single crystal X-ray analysis has confirmed the enolate structure. |
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