Nitridoborate

The nitridoborates are chemical compounds of boron and nitrogen with metals. These compounds are typically produced at high temperature by reacting hexagonal boron nitride (α -BN) with metal nitrides or by metathesis reactions involving nitridoborates. A wide range of these compounds have been made involving lithium, alkaline earth metals and lanthanides, and their structures determined using crystallographic techiques such as X-ray crystallography. Structurally one of their interesting features is the presence of polyatomic anions of boron and nitrogen where the geometry and the B-N bond length have been interpreted in terms of π-bonding. Many of the compounds produced can be described as ternary compounds of metal boron and nitrogen and examples of these are Li3BN2, Mg3BN3, La3B3N6, La5B4N9.[1] However there are examples of compounds with more than one metal, for example La3Ni2B2N3[2] and compounds containing anions such as Cl−, for example Mg2BN2Cl.[3]

Structures and bonding

Examination of the crystallographic data shows the presence of polyatomic units consisting of boron and nitrogen. These units have structures similar to those of isoelectronic anions, which have π-bonded structures. The bonding in some of these compounds is ionic in character, such as Ca3[BN2]2, other compounds have metallic characteristics, where the bonding has been described in terms of π-bonded anions with extra electrons in anti-bonding orbitals that not only cause a lengthening of the B-N bonds but also form part of the conduction band of the solid.[4] The simplest ion BNn− is comparable to the C22− ion, but attempts to prepare the compound CaBN analogous to CaC2 calcium carbide failed. The bonding of compounds containing the diatomic BN anion have been explained in terms of electrons entering anti-bonding orbitals and reducing the B-N bond order from 3 (triple bond) in BN2− to 2 (double bond) in BN4−.[5]

Some nitridoborates are salt-like such as Li3BN2, LiCa4[BN2]3 others have a metallic lustre, such as LiEu4[BN2]3. Bonding calculations show that the energy of the valence orbitals of metal atoms of group 2 and lanthanide elements are higher than those of the bonding orbitals in BNx ions which indicates an ionic like interaction between a metal atom and a BNx ion. With lanthanide compounds where extra electrons enter the anti-bonding orbitals of an ion there can be a smaller band gap giving the compounds metal like properties such as lustre. With transition metals the d orbitals can be similar in energy to bonding orbitals in the BN anions suggesting covalent interactions.[4]

anion geometry Typical B-N bond length (pm) B-B bond length (pm)isoelectronic withExamples of compounds
BNn−linear 138 - 202[5][6][7] CaNiBN,(Ca2+Ni2+BN4−); LaNiBN, (La3+Ni2+BN4−(e−))
BN23− linear 132 - 137[4][8] [CN2]2−, CO2Ca3(BN2)2
BN36− trigonal planar 145 - 149[4][7] BO33−, CO32−La6(BN3)O6
B2N48− planar 147 - 150[4]177 - 182[4] C2O42−La3B2N4, ((La3+)3(B2N48−)(e−))
B3N69− planar or chair form 144 - 151[4] La3B3N6[9]

For comparison purposes the following are considered to be typical BN bond lengths[1]

Compound B-N (pm) Bond type
Me3N·BBr3 160.2 single
Me3N·BCl3 157.5 single
Cubic-BN 157 Single
Hexagonal-BN 144.6 intra-layer distance some π-bonding
B(NMe2)3 143.9 some π-bonding
Mes2BNBMes2 134.5 double bond
(tBu)BN(tBu) 125.8 triple bond

Mes= 2,4,6 Me3C6H2

References

  1. 1 2 Housecroft, Catherine E; Sharpe, Alan G (2005). Inorganic Chemistry (2d ed.). Pearson education. p. 318. ISBN 978-0-13-039913-7.
  2. ↑ Blaschkowski, Björn; Meyer, H.-Jürgen (2003). "X-Ray Single Crystal Refinement and Superconductivity of La3Ni2B2N3". Zeitschrift für anorganische und allgemeine Chemie 629 (1): 129–132. doi:10.1002/zaac.200390004. ISSN 0044-2313.
  3. ↑ Somer, Mehmet; Kütükcü, Mehmet Nuri; Gil, Raul Cardoso; Borrmann, Horst; Carrillo-Cabrera, Wilder (2004). "Mg2[BN2]Cl and Mg8[BN2]5I: Novel Magnesium Nitridoborate Halides— Syntheses, Crystal Structures, and Vibrational Spectra". Zeitschrift für anorganische und allgemeine Chemie 630 (7): 1015–1021. doi:10.1002/zaac.200400055. ISSN 0044-2313.
  4. 1 2 3 4 5 6 7 Meyer, H. Jurgen (2006). "Chapter 8: Current State on (B,C,N) compounds of Calcium and Lanthanum". In Meyer, Gerd; Naumann, Dieter; Wesemann, Lars. Inorganic Chemistry in Focus III. Wiley-VCH. pp. 121–138. ISBN 978-3-527-31510-9.
  5. 1 2 Blaschkowski, Björn; Meyer, H.-Jürgen (2002). "Electronic Conditions of Diatomic (BN) Anions in the Structure of CaNiBN". Zeitschrift für anorganische und allgemeine Chemie 628 (6): 1249. doi:10.1002/1521-3749(200206)628:6<1249::AID-ZAAC1249>3.0.CO;2-S. ISSN 0044-2313.
  6. ↑ Cava, R. J.; Zandbergen, H. W.; Batlogg, B.; Eisaki, H.; Takagi, H.; Krajewski, J. J.; Peck, W. F.; Gyorgy, E. M.; Uchida, S. (1994). "Superconductivity in lanthanum nickel boro-nitride". Nature 372 (6503): 245–247. doi:10.1038/372245a0. ISSN 0028-0836.
  7. 1 2 Blaschkowski, Björn; Jing, Haipeng; Meyer, H.-Jürgen (2002). "Nitridoborates of the Lanthanides: Synthesis, Structure Principles, and Properties of a New Class of Compounds". Angewandte Chemie International Edition 41 (18): 3322–3336. doi:10.1002/1521-3773(20020916)41:18<3322::AID-ANIE3322>3.0.CO;2-8. ISSN 1433-7851.
  8. ↑ Somer, Mehmet; Herterich, Uwe; Čurda, Jan; Carrillo-Cabrera, Wilder; Zürn, Anke; Peters, Karl; Schnering, Hans Georg von (2000). "Darstellung, Kristallstrukturen und Schwingungsspektren neuer ternärer Verbindungen mit dem Anion [N-B-N]3-". Zeitschrift für anorganische und allgemeine Chemie 626 (3): 625–633. doi:10.1002/(SICI)1521-3749(200003)626:3<625::AID-ZAAC625>3.0.CO;2-4. ISSN 0044-2313.
  9. ↑ Reckeweg, Olaf; Meyer, H.-Jürgen (1999). "Lanthanoidnitridoborate mit sechsgliedrigen B3N6-Ringen: Ln3B3N6". Angewandte Chemie 111 (11): 1714–1716. doi:10.1002/(SICI)1521-3757(19990601)111:11<1714::AID-ANGE1714>3.0.CO;2-X. ISSN 0044-8249.
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