TY - JOUR
T1 - Iron-Containing Metallophosphazenes and Their Clusters Derived from Chlorophosphazenes and Organometallic Dianions
AU - AJlcock, Harry R.
AU - Suszko, Paul R.
AU - Wagner, Linda J.
AU - Whittle, Robert R.
AU - Boso, Brian
PY - 1984/8/1
Y1 - 1984/8/1
N2 - Hexachlorocyclotriphosphazene, (NPC12)3, reacts with disodium octacarbonyldiferrate, Na2Fe2(CO)8, to yield the diiron and triiron cyciotriphosphazene complexes 2 and 3, respectively. The analogous cyclic tetramer (NPC12)4 reacts similarly to yield the diiron and triiron analogues 5 and 6, respectively. Compounds 2 and 5 are the first chlorophosphazenes that contain two metal-phosphorus covalent bonds and a three-membered spirocyclic ring at phosphorus. Compound 3 can also be obtained by the thermal reaction of 2 with the neutral carbonyl complexes Fe(CO)5 and Fe2(CO)9. In addition, the thermal reaction of 2 with Ru3(CO)12 yields the mixed-metal cluster 7, similar in structure to 3, but with a Ru(CO)3 unit in place of the nitrogen-bound Fe(CO)3. The trimetallic clusters 3, 6, and 7 are the first phosphazene compounds in which a portion of the phosphazene ring has been incorporated into a metallic cluster unit. Compounds 3, 6, and 7 contain both phosphorus-metal and nitrogen-metal bonds, demonstrating both the covalent and coordinative capacities of phosphazene rings. The new metallophosphazenes were characterized by 31P NMR, Mössbauer, infrared, and mass spectral techniques and by X-ray crystal structure analyses.
AB - Hexachlorocyclotriphosphazene, (NPC12)3, reacts with disodium octacarbonyldiferrate, Na2Fe2(CO)8, to yield the diiron and triiron cyciotriphosphazene complexes 2 and 3, respectively. The analogous cyclic tetramer (NPC12)4 reacts similarly to yield the diiron and triiron analogues 5 and 6, respectively. Compounds 2 and 5 are the first chlorophosphazenes that contain two metal-phosphorus covalent bonds and a three-membered spirocyclic ring at phosphorus. Compound 3 can also be obtained by the thermal reaction of 2 with the neutral carbonyl complexes Fe(CO)5 and Fe2(CO)9. In addition, the thermal reaction of 2 with Ru3(CO)12 yields the mixed-metal cluster 7, similar in structure to 3, but with a Ru(CO)3 unit in place of the nitrogen-bound Fe(CO)3. The trimetallic clusters 3, 6, and 7 are the first phosphazene compounds in which a portion of the phosphazene ring has been incorporated into a metallic cluster unit. Compounds 3, 6, and 7 contain both phosphorus-metal and nitrogen-metal bonds, demonstrating both the covalent and coordinative capacities of phosphazene rings. The new metallophosphazenes were characterized by 31P NMR, Mössbauer, infrared, and mass spectral techniques and by X-ray crystal structure analyses.
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U2 - 10.1021/ja00329a057
DO - 10.1021/ja00329a057
M3 - Article
AN - SCOPUS:0021479790
VL - 106
SP - 4966
EP - 4977
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 17
ER -