The structures of five organonickel compounds were determined using x-ray diffraction techniques. This study was conducted to ascertain the relationships between the compound's structures, bonding, and chemical properties. The first structural evidence for discrete complexes containing Ni-SiX3 bonds is (h6-mesitylene)Ni(SiCl3)2 and presented. The compounds (h6-toluene)Ni(SiF3)2, crystallize in space group P21/c with Z = 2. The lattice constants at 23° C are: a = 9.056(2), b = 14.426(1), c = 13. 3 0 3 ( 2) ~, {J = 10 0. 6 9 ( 1 )0 , and a = 11. 3 5 5 ( 3) , b = 11.268(4), c = 14.326(8)~, and {J = 140.97(8)0 for the compounds, respectively. Both structures exhibit short Ni-Si bond distances and planar arenes, with other bond parameters similarly indicating significant Ni-to-SiX3 pi back-bonding. The SiF3 ligands are shown to be much better pi-acids than the SiCl3 groups. The most striking evidence for this is the unprecidented short Ni-SiF3 bond distance of 2.154(3)~ and the predictably short nickel to arene distance of 1.643(3)~ in (h6-toluene)Ni(SiF3)2. The analogous Ni-SiCl3 bond distance in (h6-mesitylene)Ni(SiCl3)2 is 2.194(1)~ while the nickel to arene-plane distance is 1.697(1)~.
Analysis of (C0)3Ni(SiCl3)2 revealed a long axial Ni-Si bond distance of 2.286(3)~ in the trigonal bipyramidal complex. The compound crystallizes in space group P21/c with Z = 2, with lattice constants at 25°C of: a= 9.709(8), b = 22.65(2), c = 6.731(5)~, and {J = 75.76(5)0 • The compound (H9C4S)2Ni(C6F5)2, crystallizes in space group P21/c with z = 2, with the Ni residing on a crystallographic center of inversion. The lattice constants at 23°C are: a= 10.698(3), b = 11.246(3), c = 9.561(2)~, and {J = 106.78(2). The Ni-C6F5 bond distance of 2.196(3)A indicates a reasonably strong bonding interaction without any appreciable Ni-to-C6F5 pi back-bonding. The compound [(h5-C5H5)Ni(C6F5)2] [(H5C2)4N] crystallizes with two formula units per unit cell in space group Pl, with lattice constants at 23° C of: a = 14.306(2), b = 0.930<1>, c = l0.599(2>A, a = 96.s1, and ry = 90.61(1)0 • The pi-Cp has a significant non-planar deformation attributable to electronic factors. -
","abstract_html":"<p>The structures of five organonickel compounds were determined using x-ray diffraction techniques. This study was conducted to ascertain the relationships between the compound's structures, bonding, and chemical properties. The first structural evidence for discrete complexes containing Ni-SiX3 bonds is (h6-mesitylene)Ni(SiCl3)2 and presented. The compounds (h6-toluene)Ni(SiF3)2, crystallize in space group P21/c with Z = 2. The lattice constants at 23° C are: a = 9.056(2), b = 14.426(1), c = 13. 3 0 3 ( 2) ~, {J = 10 0. 6 9 ( 1 )0 , and a = 11. 3 5 5 ( 3) , b = 11.268(4), c = 14.326(8)~, and {J = 140.97(8)0 for the compounds, respectively. Both structures exhibit short Ni-Si bond distances and planar arenes, with other bond parameters similarly indicating significant Ni-to-SiX3 pi back-bonding. The SiF3 ligands are shown to be much better pi-acids than the SiCl3 groups. The most striking evidence for this is the unprecidented short Ni-SiF3 bond distance of 2.154(3)~ and the predictably short nickel to arene distance of 1.643(3)~ in (h6-toluene)Ni(SiF3)2. The analogous Ni-SiCl3 bond distance in (h6-mesitylene)Ni(SiCl3)2 is 2.194(1)~ while the nickel to arene-plane distance is 1.697(1)~.</p> <p>Analysis of (C0)3Ni(SiCl3)2 revealed a long axial Ni-Si bond distance of 2.286(3)~ in the trigonal bipyramidal complex. The compound crystallizes in space group P21/c with Z = 2, with lattice constants at 25°C of: a= 9.709(8), b = 22.65(2), c = 6.731(5)~, and {J = 75.76(5)0 • The compound (H9C4S)2Ni(C6F5)2, crystallizes in space group P21/c with z = 2, with the Ni residing on a crystallographic center of inversion. The lattice constants at 23°C are: a= 10.698(3), b = 11.246(3), c = 9.561(2)~, and {J = 106.78(2). The Ni-C6F5 bond distance of 2.196(3)A indicates a reasonably strong bonding interaction without any appreciable Ni-to-C6F5 pi back-bonding. The compound [(h5-C5H5)Ni(C6F5)2] [(H5C2)4N] crystallizes with two formula units per unit cell in space group Pl, with lattice constants at 23° C of: a = 14.306(2), b = 0.930<1>, c = l0.599(2>A, a = 96.s1, and ry = 90.61(1)0 • The pi-Cp has a significant non-planar deformation attributable to electronic factors. -</p>","abstract_has_math":false,"creators":["Janikowski, Stuart Kevin"],"institution":null,"degree_name":"Doctor of Philosophy (PhD)","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Dr. Lewis J. Radonovich"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1985,"date_issued":"1985-08-01T07:00:00Z","date_published":"1985-08-01T07:00:00Z","updated_at":"2026-07-24T03:25:14Z","subjects":["transition metals","organometallic compounds","complex compounds","Chemical Engineering"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://commons.und.edu/theses/415","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Dr. Lewis J. Radonovich"]},{"key":"dc:creator","label":"Author","values":["Janikowski, Stuart Kevin"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["2018-04-30T07:00:00Z"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy (PhD)"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["transition metals","organometallic compounds","complex compounds","Chemical Engineering"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://commons.und.edu/theses/415"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The structures of five organonickel compounds were determined using x-ray diffraction techniques. This study was conducted to ascertain the relationships between the compound's structures, bonding, and chemical properties. The first structural evidence for discrete complexes containing Ni-SiX3 bonds is (h6-mesitylene)Ni(SiCl3)2 and presented. The compounds (h6-toluene)Ni(SiF3)2, crystallize in space group P21/c with Z = 2. The lattice constants at 23° C are: a = 9.056(2), b = 14.426(1), c = 13. 3 0 3 ( 2) ~, {J = 10 0. 6 9 ( 1 )0 , and a = 11. 3 5 5 ( 3) , b = 11.268(4), c = 14.326(8)~, and {J = 140.97(8)0 for the compounds, respectively. Both structures exhibit short Ni-Si bond distances and planar arenes, with other bond parameters similarly indicating significant Ni-to-SiX3 pi back-bonding. The SiF3 ligands are shown to be much better pi-acids than the SiCl3 groups. The most striking evidence for this is the unprecidented short Ni-SiF3 bond distance of 2.154(3)~ and the predictably short nickel to arene distance of 1.643(3)~ in (h6-toluene)Ni(SiF3)2. The analogous Ni-SiCl3 bond distance in (h6-mesitylene)Ni(SiCl3)2 is 2.194(1)~ while the nickel to arene-plane distance is 1.697(1)~.
Analysis of (C0)3Ni(SiCl3)2 revealed a long axial Ni-Si bond distance of 2.286(3)~ in the trigonal bipyramidal complex. The compound crystallizes in space group P21/c with Z = 2, with lattice constants at 25°C of: a= 9.709(8), b = 22.65(2), c = 6.731(5)~, and {J = 75.76(5)0 • The compound (H9C4S)2Ni(C6F5)2, crystallizes in space group P21/c with z = 2, with the Ni residing on a crystallographic center of inversion. The lattice constants at 23°C are: a= 10.698(3), b = 11.246(3), c = 9.561(2)~, and {J = 106.78(2). The Ni-C6F5 bond distance of 2.196(3)A indicates a reasonably strong bonding interaction without any appreciable Ni-to-C6F5 pi back-bonding. The compound [(h5-C5H5)Ni(C6F5)2] [(H5C2)4N] crystallizes with two formula units per unit cell in space group Pl, with lattice constants at 23° C of: a = 14.306(2), b = 0.930<1>, c = l0.599(2>A, a = 96.s1, and ry = 90.61(1)0 • The pi-Cp has a significant non-planar deformation attributable to electronic factors. -
"]},{"key":"dc:title","label":"Title","values":["A Structural Study of Some (h6-Arene)ML2, First Row, Group VIII, Transition Metal Complexes and Their Derivatives"]}]}],"canonical_facts":{"dc:contributor":["Dr. Lewis J. Radonovich"],"dc:creator":["Janikowski, Stuart Kevin"],"dc:date.available":["2018-04-30T07:00:00Z"],"dc:description.abstract":["The structures of five organonickel compounds were determined using x-ray diffraction techniques. This study was conducted to ascertain the relationships between the compound's structures, bonding, and chemical properties. The first structural evidence for discrete complexes containing Ni-SiX3 bonds is (h6-mesitylene)Ni(SiCl3)2 and presented. The compounds (h6-toluene)Ni(SiF3)2, crystallize in space group P21/c with Z = 2. The lattice constants at 23° C are: a = 9.056(2), b = 14.426(1), c = 13. 3 0 3 ( 2) ~, {J = 10 0. 6 9 ( 1 )0 , and a = 11. 3 5 5 ( 3) , b = 11.268(4), c = 14.326(8)~, and {J = 140.97(8)0 for the compounds, respectively. Both structures exhibit short Ni-Si bond distances and planar arenes, with other bond parameters similarly indicating significant Ni-to-SiX3 pi back-bonding. The SiF3 ligands are shown to be much better pi-acids than the SiCl3 groups. The most striking evidence for this is the unprecidented short Ni-SiF3 bond distance of 2.154(3)~ and the predictably short nickel to arene distance of 1.643(3)~ in (h6-toluene)Ni(SiF3)2. The analogous Ni-SiCl3 bond distance in (h6-mesitylene)Ni(SiCl3)2 is 2.194(1)~ while the nickel to arene-plane distance is 1.697(1)~.
Analysis of (C0)3Ni(SiCl3)2 revealed a long axial Ni-Si bond distance of 2.286(3)~ in the trigonal bipyramidal complex. The compound crystallizes in space group P21/c with Z = 2, with lattice constants at 25°C of: a= 9.709(8), b = 22.65(2), c = 6.731(5)~, and {J = 75.76(5)0 • The compound (H9C4S)2Ni(C6F5)2, crystallizes in space group P21/c with z = 2, with the Ni residing on a crystallographic center of inversion. The lattice constants at 23°C are: a= 10.698(3), b = 11.246(3), c = 9.561(2)~, and {J = 106.78(2). The Ni-C6F5 bond distance of 2.196(3)A indicates a reasonably strong bonding interaction without any appreciable Ni-to-C6F5 pi back-bonding. The compound [(h5-C5H5)Ni(C6F5)2] [(H5C2)4N] crystallizes with two formula units per unit cell in space group Pl, with lattice constants at 23° C of: a = 14.306(2), b = 0.930<1>, c = l0.599(2>A, a = 96.s1, and ry = 90.61(1)0 • The pi-Cp has a significant non-planar deformation attributable to electronic factors. -
"],"dc:identifier":["https://commons.und.edu/theses/415"],"dc:subject":["transition metals","organometallic compounds","complex compounds","Chemical Engineering"],"dc:title":["A Structural Study of Some (h6-Arene)ML2, First Row, Group VIII, Transition Metal Complexes and Their Derivatives"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Doctor of Philosophy (PhD)"]},"updated_at":"2026-07-24T03:25:14Z"}