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Synthesis and Characterization of Some Transition Metal Complexes for Homocoupling of Grignard Reagents

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Synthesis and Characterization of Some Transition Metal Complexes for Homocoupling of Grignard Reagents SYNTHESIS AND CHARACTERIZATION OF SOME TRANSITION METAL COMPLEXES FOR HOMOCOUPLING OF GRIGNARD REAGENTS Thesis Submitted in partial fulfilment of the requirements for the degree of DOCTOR OF PHILOSOPHY by APARNA P.I. DEPARTMENT OF CHEMISTRY NATIONAL INSTITUTE OF TECHNOLOGY KARNATAKA, SURATHKAL, MANGALORE - 575025 March, 2014 DECLARATION I hereby declare that the Research Thesis entitled “SYNTHESIS AND CHARACTERIZATION OF SOME TRANSITION METAL COMPLEXES FOR HOMOCOUPLING OF GRIGNARD REAGENTS” which is being submitted to the National Institute of Technology Karnataka, Surathkal in partial fulfilment of the requirements for the award of the Degree of Doctor of Philosophy in Chemistry is a bonafide report of the research work carried out by me. The material contained in this Research Thesis has not been submitted to any University or Institution for the award of any degree. Aparna P.I. Reg. No: 090703CY09F01 Department of Chemistry Place: NITK-Surathkal Date: CERTIFICATE This is to certify that the Research Thesis entitled “SYNTHESIS AND CHARACTERIZATION OF SOME TRANSITION METAL COMPLEXES FOR HOMOCOUPLING OF GRIGNARD REAGENTS” submitted by Mrs. Aparna P.I. (Register Number: 090703CY09F01) as the record of the research work carried out by her, is accepted as the Research Thesis submission in partial fulfilment of the requirements for the award of degree of Doctor of Philosophy. Research Guide Chairman - DRPC DEDICATION I am dedicating my thesis to my loving parents, P. Parameshwari and P. Ishwara Bhat who are my soul, strength and life. Without whom I could not have made it here. Their endless love, support and confidence kept me working when I wanted to give up. This thesis is dedicated to the memory of my Late grandmother, Rathnamma, who raised me and taught me to speak. Her love, care, strength, thirst for education and faith in me till the last moment of her life gave me a new appreciation for the meaning and importance of 'education.' I am dedicating my thesis to my grandparents Late Panjigadde Ramakrishna Bhat-Late Shankari amma, Late Panjaje Shankara Bhat-Late Savithri amma and I am dedicating this thesis to my dearest uncle Late P.S. Vijayashankar. Their memories continue to regulate my life. I am dedicating the thesis to my beloved in-laws, Shashiprabha and Mahalingeshwara Bhat whose understanding, love, care and faith throughout my research life made it possible today. This thesis would be incomplete without a mention of the support given to me by my cherished husband, Dr. Harisha Kinilakodi, to whom this thesis is dedicated. He was my own "soul out of my soul," who kept my spirits up when the muses failed me. Without his unconditional support when this thesis seemed interminable, I doubt it would ever have been completed. I am dedicating my work to my beloved brother Shrikrishna P.I., who is my strength, best friend, mentor, guide and cheerleader. I dedicate thesis to my sisters Usha and Dr. Chethana, brother-in-laws Shivashankara Bhat and Dr. Ramachandra Bhat for their support, encouragement and care. I dedicate this thesis to my cousin brother Tushar, for being with me throughout my work with love and support. I am dedicating my work to my brothers Anish and Ashok who encouraged me throughout my work. I am dedicating my work to my nephew Shwetha, Swathi and Anirudh who brought smile and joy in my life. I am dedicating my thesis to all my well wishers, especially, S. Venkatramana Bhat, Shankari amma, Parameshwara Bhat K.R., Sharada K., Govinda Bhat, Veena Govinda Bhat, Kaushal, all Panjaje-P.S brothers, Pattaje Lakshmi amma, Kinilakodi Gopalakrishna Bhat, Panjigudde Saraswathi, Jayashree Tondamoole, Gokul Shet, Bhaskara Upadhyaya, Muruva Subramanya Bhat, Late H. Shankara Bhat for constant support and encouragement. My special dedication to V. Raveeshanna for his endless love and care. I am dedicating my thesis to my research guide, Dr. B. Ramachandra Bhat for opening my eyes, without whom my dream could not have come true today. I am dedicating this thesis to my Acharya Dr. B. Shridhara Bhat and Savithri Shridhara Bhat for their countless love and care, who inspired my life in all the ways. I am dedicating this thesis to Padaru Narayana Bhat and P.N. Ambika amma who blessed me with a scholarship and motivated me to persue higher education. I am dedicating my thesis to Jalli Ishwara Bhat who lightened my life when I was in dark. I am dedicating my thesis to all my teachers, especially to Yamuna teacher, Vadva Venkatramana Bhat, Late Rajashekhar Rao, Dr. Arun Prakash, Dr. A.P. Radhakrishna and Chandrashekhar Kalchar, who made me what I am today. I am dedicating this thesis to all my good friends who helped me in good and bad. Especially to Sathish Naik, Rayan, Rajesh, Rammi, Mahesha Poojary, Sandya Rani, Rakesh Kumar Kammaje, Adarsh Hegde, Sarita Alva, Prasad Ananthady, Chaithra, Srijana and Supriya who have been waiting to see their 'appu' as 'Dr. Aparna'. Finally, at the most, I am dedicating my thesis to the 'Shree Peeta' and the Almighty 'Goddess Devi' for always being with me in all the ways. ACKNOWLEDGEMENTS It gives me immense pleasure to express my heartfelt gratitude to my mentor, philosopher and research guide Prof. B. Ramachandra Bhat, Head of the Department, for his insightful guidance, continued inspiration and extreme patience over the years, which made this study possible. I am very much grateful for his unwavering support, invaluable suggestions, generous advice, constructive criticism, balanced approach towards success and failure throughout the study. It was refreshing to work for and with a professional of such a high caliber. It was great experience to learn many aspects from him both as a teacher and a human being. I would also like to thank my RPAC committee members: Prof. Mahesha A., Department of Applied Mechanics and Prof. D. Krishna Bhat, Department of Chemistry, for spending their valuable time and energy in evaluating my progress and providing thoughtful suggestions. A special gratitude to Prof. A. Chitharanjan Hegde for motivating me to take-up the research. I have learnt many things from him as a great human being. I sincerely acknowledge Prof. A. Nithyananda Shetty, Prof. A. Vasudeva Adhikari, Prof. D. Krishna Bhat, Dr. Arun M. Isloor, Dr. D. Uday Kumar and Dr. Darshak R. Trivedi for their continuous encouragement and co-operation. I am grateful to National Institute of Technology Karnataka, Surathkal for providing me research fellowship which made this work possible. I thank Indian Institute of Science, Bangalore for NMR analysis. I would like to thank Head of Department of Chemical Engineering, NITK Surathkal for providing TG and UV analysis throughout my research work. A special thanks to my good friend Miss. Reshma Kayarmar, who helped me in carrying out mass analysis of all my samples. I would like to mention a word of gratitude to my friend Mrs. Sandya Rani for her help throughout my research work. Whenever I was low, needed a help she was there. I also thank Dr. Ravi K, Dr. Vishnumoorthy, Dr. Shridhar Malladi, Dr. Murali, Dr. Santhosh, Dr. Sunitha, Dr. Arthi, Vishwanath, Dr. Sujaya, Trithila and Kalaivani for helping me in various stages with fruitful discussions. Special thanks to Shwetha Panjigadde (IISc) and my best friend Adarsh Hegde (IISc) for helping me in providing the literature whenever I needed throughout my work and for their valuable assistance. I am very thankful to my fellow researchers for helping me in various stages of this research work. A special thanks to Dr. Ramasubramanian, Dr. Dileep, Dr. Rudresh, Dr. Sampath Kumar, Dr. Ravindra, Mr. Aravinda, Miss. Pooja, Mr. Raghavendra Prasad, Mrs. Lolakshi and Miss. Ansari Rasheeda Maqbool for their good support and cooperation. I am grateful to the non-teaching staff, Mr. Ashok, Mrs. Kasthuri, Mr. Prashanth, Mr. Pradeep, Mr. Harish, Mrs. Shilpa Kunder, Mrs. Sharmila, Mrs. Deepa and Mrs. Usha who were prompt enough to lend me a helping hand at times of need. The time spent at NITK was dominated by happy moments. Thanks to all the scholar friends for making my research days at NITK a fun-filled and memorable one. I whole heartedly thank each one of them and wish them success in their research work and all future endeavors. My intellectual debt is to Mahesha Poojary, Selvam, Raghavendra, Vinay, Suhasini, Lekha, Ranjana, Chinmayi, Swathi and Veena for all the support, cooperation and life experience. They made my stay in NITK more memorable and meaningful. My special feeling of gratitude to all my teachers-since my childhood till today, because of whom what I am today. I indebt to Dr. B. Shridhara Bhat, Vadva Venkatramana Bhat, Late H.V. Rajashekhar Rao, Prof. M.S. Bhat, Chandrashekhara Kalchar, Dr. Arun Prakash, Adarsha Chokkady, Yamuna teacher for all the inspiration, guidance, care and support given to me throughout my work. I owe my deepest gratitude to Smt. Savithri Shridhara Bhat, Dr. Poornima Ramachandra and Smt. Sunanda Chittaranjan Hegde for their moral support, love and care. I would like to show my greatest appreciation to my childhood friends, Sathish Naik, Rayon Antony D'souza, Rajesh Nayak, Rammi for being with me in all the way. I owe a very important debt to my good friends Rakesh Kumar Kammaje, Sarita Alva, Prasad Ananthady, Chaithra, Srijana, Supriya for all the love and support given to me. I would like to acknowledge my family members for their unconditional support, understanding, confidence, care and love, especially, my parents, P. Parameshwari-P. Ishwara Bhat; in-laws, Shashiprabha-K. Mahalingeshwara Bhat; brother Shrikrishna P.I; Sisters, Usha, Chethana; brother-in-law, Shivashankara Bhat, Ramachandra Bhat; nephew, Shwetha, Swathi, Anirudh; Cousin brother, Tushar; brothers, Anish, Ashok; well wishers; S. Venkatramana Bhat, K.R. Parameshwara Bhat, Shankari amma, Sharada, Bhaskara Upadhyaya, Dr.
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