Binary Group 15 Polyazides. Structural Characterization of [Bi(N3)4]−, [Bi(N3)5]2–, [bipy·Bi(N3)5]2–, [Bi(N3)6]3–, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2 and on the Lone Pair Activation of Valence Electrons

The binary group 15 polyazides As(N3)3, Sb(N3)3, and Bi(N3)3 were stabilized by either anion or donor−acceptor adduct formation. Crystal structures are reported for [Bi(N3)4]–, [Bi(N3)5]2–, [bipy·Bi(N3)5]2–, [Bi(N3)6]3–, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2. The lone valence electron p...

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Veröffentlicht in:Inorganic chemistry 2012-01, Vol.51 (2), p.1127-1141
Hauptverfasser: Haiges, Ralf, Rahm, Martin, Dixon, David A, Garner, Edward B, Christe, Karl O
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Dixon, David A
Garner, Edward B
Christe, Karl O
description The binary group 15 polyazides As(N3)3, Sb(N3)3, and Bi(N3)3 were stabilized by either anion or donor−acceptor adduct formation. Crystal structures are reported for [Bi(N3)4]–, [Bi(N3)5]2–, [bipy·Bi(N3)5]2–, [Bi(N3)6]3–, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2. The lone valence electron pair on the central atom of these pnictogen(+III) compounds can be either sterically active or inactive. The [Bi(N3)5]2– anion possesses a sterically active lone pair and a monomeric pseudo-octahedral structure with a coordination number of 6, whereas its 2,2′-bipyridine adduct exhibits a pseudo-monocapped trigonal prismatic structure with CN 7 and a sterically inactive lone pair. Because of the high oxidizing power of Bi(+V), reactions aimed at Bi(N3)5 and [Bi(N3)6]– resulted in the reduction to bismuth(+III) compounds by [N3]–. The powder X-ray diffraction pattern of Bi(N3)3 was recorded at 298 K and is distinct from that calculated for Sb(N3)3 from its single-crystal data at 223 K. The [(bipy)2·Bi(N3)3]2 adduct is dimeric and derived from two BiN8 square antiprisms sharing an edge consisting of two μ1,1-bridging N3 ligands and with bismuth having CN 8 and a sterically inactive lone pair. The novel bipy·As(N3)3 and bipy·Sb(N3)3 adducts are monomeric and isostructural and contain a sterically active lone pair on their central atom and a CN of 6. A systematic quantum chemical analysis of the structures of these polyazides suggests that the M06-2X density functional is well suited for the prediction of the steric activity of lone pairs in main-group chemistry. Furthermore, it was found that the solid-state structures can strongly differ from those of the free gas-phase species or those in solutions and that lone pairs that are sterically inactive in a chemical surrounding can become activated in the free isolated species.
doi_str_mv 10.1021/ic202307a
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Structural Characterization of [Bi(N3)4]−, [Bi(N3)5]2–, [bipy·Bi(N3)5]2–, [Bi(N3)6]3–, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2 and on the Lone Pair Activation of Valence Electrons</title><source>ACS Publications</source><creator>Haiges, Ralf ; Rahm, Martin ; Dixon, David A ; Garner, Edward B ; Christe, Karl O</creator><creatorcontrib>Haiges, Ralf ; Rahm, Martin ; Dixon, David A ; Garner, Edward B ; Christe, Karl O</creatorcontrib><description>The binary group 15 polyazides As(N3)3, Sb(N3)3, and Bi(N3)3 were stabilized by either anion or donor−acceptor adduct formation. Crystal structures are reported for [Bi(N3)4]–, [Bi(N3)5]2–, [bipy·Bi(N3)5]2–, [Bi(N3)6]3–, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2. The lone valence electron pair on the central atom of these pnictogen(+III) compounds can be either sterically active or inactive. The [Bi(N3)5]2– anion possesses a sterically active lone pair and a monomeric pseudo-octahedral structure with a coordination number of 6, whereas its 2,2′-bipyridine adduct exhibits a pseudo-monocapped trigonal prismatic structure with CN 7 and a sterically inactive lone pair. Because of the high oxidizing power of Bi(+V), reactions aimed at Bi(N3)5 and [Bi(N3)6]– resulted in the reduction to bismuth(+III) compounds by [N3]–. The powder X-ray diffraction pattern of Bi(N3)3 was recorded at 298 K and is distinct from that calculated for Sb(N3)3 from its single-crystal data at 223 K. The [(bipy)2·Bi(N3)3]2 adduct is dimeric and derived from two BiN8 square antiprisms sharing an edge consisting of two μ1,1-bridging N3 ligands and with bismuth having CN 8 and a sterically inactive lone pair. The novel bipy·As(N3)3 and bipy·Sb(N3)3 adducts are monomeric and isostructural and contain a sterically active lone pair on their central atom and a CN of 6. 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Structural Characterization of [Bi(N3)4]−, [Bi(N3)5]2–, [bipy·Bi(N3)5]2–, [Bi(N3)6]3–, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2 and on the Lone Pair Activation of Valence Electrons</title><title>Inorganic chemistry</title><addtitle>Inorg. Chem</addtitle><description>The binary group 15 polyazides As(N3)3, Sb(N3)3, and Bi(N3)3 were stabilized by either anion or donor−acceptor adduct formation. Crystal structures are reported for [Bi(N3)4]–, [Bi(N3)5]2–, [bipy·Bi(N3)5]2–, [Bi(N3)6]3–, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2. The lone valence electron pair on the central atom of these pnictogen(+III) compounds can be either sterically active or inactive. The [Bi(N3)5]2– anion possesses a sterically active lone pair and a monomeric pseudo-octahedral structure with a coordination number of 6, whereas its 2,2′-bipyridine adduct exhibits a pseudo-monocapped trigonal prismatic structure with CN 7 and a sterically inactive lone pair. Because of the high oxidizing power of Bi(+V), reactions aimed at Bi(N3)5 and [Bi(N3)6]– resulted in the reduction to bismuth(+III) compounds by [N3]–. The powder X-ray diffraction pattern of Bi(N3)3 was recorded at 298 K and is distinct from that calculated for Sb(N3)3 from its single-crystal data at 223 K. The [(bipy)2·Bi(N3)3]2 adduct is dimeric and derived from two BiN8 square antiprisms sharing an edge consisting of two μ1,1-bridging N3 ligands and with bismuth having CN 8 and a sterically inactive lone pair. The novel bipy·As(N3)3 and bipy·Sb(N3)3 adducts are monomeric and isostructural and contain a sterically active lone pair on their central atom and a CN of 6. A systematic quantum chemical analysis of the structures of these polyazides suggests that the M06-2X density functional is well suited for the prediction of the steric activity of lone pairs in main-group chemistry. 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Structural Characterization of [Bi(N3)4]−, [Bi(N3)5]2–, [bipy·Bi(N3)5]2–, [Bi(N3)6]3–, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2 and on the Lone Pair Activation of Valence Electrons</title><author>Haiges, Ralf ; Rahm, Martin ; Dixon, David A ; Garner, Edward B ; Christe, Karl O</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a244t-495b2b377f56dabe5ee2675fcab25d6e49263f279e25b0a84d2a4a17425b99503</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2012</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Haiges, Ralf</creatorcontrib><creatorcontrib>Rahm, Martin</creatorcontrib><creatorcontrib>Dixon, David A</creatorcontrib><creatorcontrib>Garner, Edward B</creatorcontrib><creatorcontrib>Christe, Karl O</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Haiges, Ralf</au><au>Rahm, Martin</au><au>Dixon, David A</au><au>Garner, Edward B</au><au>Christe, Karl O</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Binary Group 15 Polyazides. Structural Characterization of [Bi(N3)4]−, [Bi(N3)5]2–, [bipy·Bi(N3)5]2–, [Bi(N3)6]3–, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2 and on the Lone Pair Activation of Valence Electrons</atitle><jtitle>Inorganic chemistry</jtitle><addtitle>Inorg. Chem</addtitle><date>2012-01-16</date><risdate>2012</risdate><volume>51</volume><issue>2</issue><spage>1127</spage><epage>1141</epage><pages>1127-1141</pages><issn>0020-1669</issn><eissn>1520-510X</eissn><abstract>The binary group 15 polyazides As(N3)3, Sb(N3)3, and Bi(N3)3 were stabilized by either anion or donor−acceptor adduct formation. Crystal structures are reported for [Bi(N3)4]–, [Bi(N3)5]2–, [bipy·Bi(N3)5]2–, [Bi(N3)6]3–, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2. The lone valence electron pair on the central atom of these pnictogen(+III) compounds can be either sterically active or inactive. The [Bi(N3)5]2– anion possesses a sterically active lone pair and a monomeric pseudo-octahedral structure with a coordination number of 6, whereas its 2,2′-bipyridine adduct exhibits a pseudo-monocapped trigonal prismatic structure with CN 7 and a sterically inactive lone pair. Because of the high oxidizing power of Bi(+V), reactions aimed at Bi(N3)5 and [Bi(N3)6]– resulted in the reduction to bismuth(+III) compounds by [N3]–. The powder X-ray diffraction pattern of Bi(N3)3 was recorded at 298 K and is distinct from that calculated for Sb(N3)3 from its single-crystal data at 223 K. The [(bipy)2·Bi(N3)3]2 adduct is dimeric and derived from two BiN8 square antiprisms sharing an edge consisting of two μ1,1-bridging N3 ligands and with bismuth having CN 8 and a sterically inactive lone pair. The novel bipy·As(N3)3 and bipy·Sb(N3)3 adducts are monomeric and isostructural and contain a sterically active lone pair on their central atom and a CN of 6. A systematic quantum chemical analysis of the structures of these polyazides suggests that the M06-2X density functional is well suited for the prediction of the steric activity of lone pairs in main-group chemistry. Furthermore, it was found that the solid-state structures can strongly differ from those of the free gas-phase species or those in solutions and that lone pairs that are sterically inactive in a chemical surrounding can become activated in the free isolated species.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>22221015</pmid><doi>10.1021/ic202307a</doi><tpages>15</tpages></addata></record>
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title Binary Group 15 Polyazides. Structural Characterization of [Bi(N3)4]−, [Bi(N3)5]2–, [bipy·Bi(N3)5]2–, [Bi(N3)6]3–, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2 and on the Lone Pair Activation of Valence Electrons
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