The Intermetalloid Clusters [Ni2Bi12]4+ and [Rh2Bi12]4+ – Ionothermal Synthesis, Crystal Structures, and Chemical Bonding
The intermetalloid clusters [M2Bi12]4+ (M = Ni, Rh) were synthesized as halogenido‐aluminates in Lewis‐acidic ionic liquids. The reaction of bismuth and NiCl2 in [BMIm]Cl·5AlCl3 (BMIm = 1‐butyl‐3‐methylimidazolium) at 180 °C yielded black, triclinic (P1) crystals of [Ni2Bi12][AlCl4]3[Al2Cl7]. Black,...
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| Veröffentlicht in: | Zeitschrift für anorganische und allgemeine Chemie (1950) 2019-02, Vol.645 (3), p.161-169 |
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| container_title | Zeitschrift für anorganische und allgemeine Chemie (1950) |
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| creator | Groh, Matthias F. Müller, Ulrike Isaeva, Anna Ruck, Michael |
| description | The intermetalloid clusters [M2Bi12]4+ (M = Ni, Rh) were synthesized as halogenido‐aluminates in Lewis‐acidic ionic liquids. The reaction of bismuth and NiCl2 in [BMIm]Cl·5AlCl3 (BMIm = 1‐butyl‐3‐methylimidazolium) at 180 °C yielded black, triclinic (P1) crystals of [Ni2Bi12][AlCl4]3[Al2Cl7]. Black, monoclinic (P21/m) crystals of [Rh2Bi12][AlBr4]4 precipitated after dissolving the cluster salt Bi12–xRhX13–x (X = Cl, Br; 0 < x < 1) in [BMIm]Br·4.1AlBr3 at 140 °C. In the cationic cluster [Ni2Bi12]4+, the nickel atoms center two base‐sharing square antiprisms of bismuth atoms (symmetry close to D4h). The valence‐electron‐poorer rhodium‐containing cluster is a distorted variant of this motif: the terminating Bi4 rings are folded to bicyclic “butterflies“ and the central square splits into two dumbbells (symmetry close to D2h). DFT‐based calculations and real‐space bonding analyses place the intermetalloid units between a triple‐decker complex and a conjoined Wade‐Mingos cluster. |
| doi_str_mv | 10.1002/zaac.201800441 |
| format | Article |
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The reaction of bismuth and NiCl2 in [BMIm]Cl·5AlCl3 (BMIm = 1‐butyl‐3‐methylimidazolium) at 180 °C yielded black, triclinic (P1) crystals of [Ni2Bi12][AlCl4]3[Al2Cl7]. Black, monoclinic (P21/m) crystals of [Rh2Bi12][AlBr4]4 precipitated after dissolving the cluster salt Bi12–xRhX13–x (X = Cl, Br; 0 < x < 1) in [BMIm]Br·4.1AlBr3 at 140 °C. In the cationic cluster [Ni2Bi12]4+, the nickel atoms center two base‐sharing square antiprisms of bismuth atoms (symmetry close to D4h). The valence‐electron‐poorer rhodium‐containing cluster is a distorted variant of this motif: the terminating Bi4 rings are folded to bicyclic “butterflies“ and the central square splits into two dumbbells (symmetry close to D2h). DFT‐based calculations and real‐space bonding analyses place the intermetalloid units between a triple‐decker complex and a conjoined Wade‐Mingos cluster.</description><identifier>ISSN: 0044-2313</identifier><identifier>EISSN: 1521-3749</identifier><identifier>DOI: 10.1002/zaac.201800441</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Aluminates ; Bismuth ; Chemical bonds ; Chemical synthesis ; Cluster compounds ; Clusters ; Coordination compounds ; Crystal structure ; Crystals ; Ionic liquids ; Nickel ; Organic chemistry ; Rhodium ; Symmetry ; Transition metals</subject><ispartof>Zeitschrift für anorganische und allgemeine Chemie (1950), 2019-02, Vol.645 (3), p.161-169</ispartof><rights>2019 WILEY‐VCH Verlag GmbH & Co. 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The reaction of bismuth and NiCl2 in [BMIm]Cl·5AlCl3 (BMIm = 1‐butyl‐3‐methylimidazolium) at 180 °C yielded black, triclinic (P1) crystals of [Ni2Bi12][AlCl4]3[Al2Cl7]. Black, monoclinic (P21/m) crystals of [Rh2Bi12][AlBr4]4 precipitated after dissolving the cluster salt Bi12–xRhX13–x (X = Cl, Br; 0 < x < 1) in [BMIm]Br·4.1AlBr3 at 140 °C. In the cationic cluster [Ni2Bi12]4+, the nickel atoms center two base‐sharing square antiprisms of bismuth atoms (symmetry close to D4h). The valence‐electron‐poorer rhodium‐containing cluster is a distorted variant of this motif: the terminating Bi4 rings are folded to bicyclic “butterflies“ and the central square splits into two dumbbells (symmetry close to D2h). DFT‐based calculations and real‐space bonding analyses place the intermetalloid units between a triple‐decker complex and a conjoined Wade‐Mingos cluster.</description><subject>Aluminates</subject><subject>Bismuth</subject><subject>Chemical bonds</subject><subject>Chemical synthesis</subject><subject>Cluster compounds</subject><subject>Clusters</subject><subject>Coordination compounds</subject><subject>Crystal structure</subject><subject>Crystals</subject><subject>Ionic liquids</subject><subject>Nickel</subject><subject>Organic chemistry</subject><subject>Rhodium</subject><subject>Symmetry</subject><subject>Transition metals</subject><issn>0044-2313</issn><issn>1521-3749</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNqFkE1LwzAcxoMoOKdXzwGP2pnXtjtuxZfBUNB5cUhI09RmdK0mLVK9-B38hn4SUybz6Cl5njy__588ABxjNMIIkfN3KdWIIBwjxBjeAQPMCQ5oxMa7YNB7AaGY7oMD51YIIYw4H4CPRaHhrGq0XetGlmVtMpiUrfOGg8sbQ6YGkyd2CmWVweVdsdXfn19wVld1U3hUlvC-q_zVGXcGE9u5prca26qmtdp7PZ4Uem2Uf5jWVWaq50Owl8vS6aPfcwgeLi8WyXUwv72aJZN5oAjyP4hVmHJM02yMtY4U1zlWDMc5Uymlqc5DlLEwzb1mlEsWUpXFEeJhmEc8ZSGnQ3Cymfti69dWu0as6tZWfqUgOCYs4hQxnxptUsrWzlmdixdr1tJ2AiPRFyz6gsW2YA-MN8CbKXX3T1o8TibJH_sDUrx_Jg</recordid><startdate>20190215</startdate><enddate>20190215</enddate><creator>Groh, Matthias F.</creator><creator>Müller, Ulrike</creator><creator>Isaeva, Anna</creator><creator>Ruck, Michael</creator><general>Wiley Subscription Services, Inc</general><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20190215</creationdate><title>The Intermetalloid Clusters [Ni2Bi12]4+ and [Rh2Bi12]4+ – Ionothermal Synthesis, Crystal Structures, and Chemical Bonding</title><author>Groh, Matthias F. ; Müller, Ulrike ; Isaeva, Anna ; Ruck, Michael</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c2021-8c6b513bd91ee7c5ef1c418f4cb33bef60d46bff4c435a463cd870566f75b4653</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Aluminates</topic><topic>Bismuth</topic><topic>Chemical bonds</topic><topic>Chemical synthesis</topic><topic>Cluster compounds</topic><topic>Clusters</topic><topic>Coordination compounds</topic><topic>Crystal structure</topic><topic>Crystals</topic><topic>Ionic liquids</topic><topic>Nickel</topic><topic>Organic chemistry</topic><topic>Rhodium</topic><topic>Symmetry</topic><topic>Transition metals</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Groh, Matthias F.</creatorcontrib><creatorcontrib>Müller, Ulrike</creatorcontrib><creatorcontrib>Isaeva, Anna</creatorcontrib><creatorcontrib>Ruck, Michael</creatorcontrib><collection>CrossRef</collection><jtitle>Zeitschrift für anorganische und allgemeine Chemie (1950)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Groh, Matthias F.</au><au>Müller, Ulrike</au><au>Isaeva, Anna</au><au>Ruck, Michael</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>The Intermetalloid Clusters [Ni2Bi12]4+ and [Rh2Bi12]4+ – Ionothermal Synthesis, Crystal Structures, and Chemical Bonding</atitle><jtitle>Zeitschrift für anorganische und allgemeine Chemie (1950)</jtitle><date>2019-02-15</date><risdate>2019</risdate><volume>645</volume><issue>3</issue><spage>161</spage><epage>169</epage><pages>161-169</pages><issn>0044-2313</issn><eissn>1521-3749</eissn><abstract>The intermetalloid clusters [M2Bi12]4+ (M = Ni, Rh) were synthesized as halogenido‐aluminates in Lewis‐acidic ionic liquids. The reaction of bismuth and NiCl2 in [BMIm]Cl·5AlCl3 (BMIm = 1‐butyl‐3‐methylimidazolium) at 180 °C yielded black, triclinic (P1) crystals of [Ni2Bi12][AlCl4]3[Al2Cl7]. Black, monoclinic (P21/m) crystals of [Rh2Bi12][AlBr4]4 precipitated after dissolving the cluster salt Bi12–xRhX13–x (X = Cl, Br; 0 < x < 1) in [BMIm]Br·4.1AlBr3 at 140 °C. In the cationic cluster [Ni2Bi12]4+, the nickel atoms center two base‐sharing square antiprisms of bismuth atoms (symmetry close to D4h). The valence‐electron‐poorer rhodium‐containing cluster is a distorted variant of this motif: the terminating Bi4 rings are folded to bicyclic “butterflies“ and the central square splits into two dumbbells (symmetry close to D2h). DFT‐based calculations and real‐space bonding analyses place the intermetalloid units between a triple‐decker complex and a conjoined Wade‐Mingos cluster.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/zaac.201800441</doi><tpages>9</tpages><oa>free_for_read</oa></addata></record> |
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| subjects | Aluminates Bismuth Chemical bonds Chemical synthesis Cluster compounds Clusters Coordination compounds Crystal structure Crystals Ionic liquids Nickel Organic chemistry Rhodium Symmetry Transition metals |
| title | The Intermetalloid Clusters [Ni2Bi12]4+ and [Rh2Bi12]4+ – Ionothermal Synthesis, Crystal Structures, and Chemical Bonding |
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