NSF Org:	CHE Division Of Chemistry
Recipient:	WASHINGTON UNIVERSITY, THE
Initial Amendment Date:	May 8, 1991
Latest Amendment Date:	June 28, 1995
Award Number:	9108130
Award Instrument:	Continuing Grant
Program Manager:	Kenneth M. Doxsee CHE  Division Of Chemistry MPS  Directorate for Mathematical and Physical Sciences
Start Date:	June 1, 1991
End Date:	November 30, 1996 (Estimated)
Total Intended Award Amount:	$728,332.00
Total Awarded Amount to Date:	$728,332.00
Funds Obligated to Date:	FY 1991 = $170,332.00 FY 1992 = $154,000.00 FY 1993 = $124,000.00 FY 1994 = $150,000.00 FY 1995 = $130,000.00
History of Investigator:	Peter Gaspar (Principal Investigator) Gaspar@wustl.edu
Recipient Sponsored Research Office:	Washington University 1 BROOKINGS DR SAINT LOUIS MO  US  63130-4862 (314)747-4134
Sponsor Congressional District:	01
Primary Place of Performance:	Washington University 1 BROOKINGS DR SAINT LOUIS MO  US  63130-4862
Primary Place of Performance Congressional District:	01
Unique Entity Identifier (UEI):	L6NFUM28LQM5
Parent UEI:
NSF Program(s):	UNIMOLECULAR PROCESSES, PROJECTS, FSU SUPPLEMENTS
Primary Program Source:	app-0193  app-0194  app-0195
Program Reference Code(s):	0000, 1942, 9161, AMPP, OTHR
Program Element Code(s):	194200, 197800, 597300
Award Agency Code:	4900
Fund Agency Code:	4900
Assistance Listing Number(s):	47.049

ABSTRACT

Various highly reactive intermediates will be generated and a study will be made of their reaction mechanisms. These highly reactive intermediates will be generated by photolysis and by pyrolysis of appropriate precursors. Decay kinetics of these species will be followed by time-resolved spectroscopy following laser flash photolysis. Chemical reactivity of these intermediates will be probed through trapping experiments and product studies. The molecules to be studied include species containing divalent silicon, germanium, and tin atoms, namely, silylenes, germylenes, and stannylenes, respectively. Reaction pathways for the monovalent six-valence-electron species nitrenes (R-N:) and phosphinidenes (R-P:), and of the monovalent four-valence-electron borylenes (R-B:) and aluminylidenes (R-Al:) will be compared with reaction paths for the corresponding carbenes, silylenes, and germylenes. Molecules will be synthesized with new kinds of bonds, including silicon-silicon and silicon-germanium triple bonds, and silicon-transition metal double bonds. New ring systems will be prepared as well. %%% This grant from the Organic Dynamics Program supports the continuing work of Professor Peter P. Gaspar at Washington University. Reactive intermediates will be generated that contain silicon, germanium, tin, phosphorous, aluminum, and boron atoms that have less than their normal complement of bonds. These reactive intermediates will be generated from stable precursor molecules by photolysis and by thermolysis methods. The steps by which these intermediates decompose will be studied as well as the rate at which these processes occur. More direct evidence for these reactive intermediates will be given by trapping them with other molecules. The products of these trapping experiments will reveal the structure of the intermediates. Compounds with silicon- silicon single and double bonds are known. Now even more reactive molecules will be synthesized with silicon-silicon and silicon- germanium triple bonds. New ring systems will also be prepared.

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