TY - JOUR

T1 - Structure and Thermal Properties of Volatile Iridium(I) Complexes with Cyclooctadiene-1,5 and β-Ketohydrazonate Ligands

AU - Karakovskaya, K. I.

AU - Vikulova, E. S.

AU - Sukhikh, T. S.

AU - Ilyin, I. Yu

AU - Morozova, N. B.

PY - 2020/1/1

Y1 - 2020/1/1

N2 - Within the search for novel promising volatile precursors for the atomic layer deposition new mixed-ligand complexes of iridium(I) with β-ketohydrazones are obtained: [Ir(cod)(dmht)] 1 and [Ir(cod)(dmha)] 2 (cod = cyclooctadiene-1,5, dmht = CF3C(O)CHC(NN(CH3)2)CH3, dmha = CH3C(O)CHC(NN(CH3)2)CH3). The compounds are characterized by the elemental analysis, IR and NMR spectroscopy, and their structures are determined by single crystal X-ray diffraction. In the complex molecules there is a distorted square coordination core IrNOC2′ (C′ is the center of the C=C bond in the cod ligand). The Ir-O, Ir-N bond lengths and Ir-C′ distances are in narrow ranges of 2.027(5)–2.039(3) Å, 2.046(6)–2.074(3) Å, and 1.982(5)–2.017(3) Å respectively. The crystal packing of 1 is of the layered type. Weak pair interactions γC-H…F are observed between the layers. The molecules of 2 form columns packed in the square motif. Shortened intermolecular contacts are not revealed in this structure. The shortest Ir…Ir distances are 5.357 A and 6.420 A in 1 and 2 structures respectively. The synthesized complexes are capable of a quantitative transition to the vapor phase (100–120 °C, 0.05 Torr) and are characterized by relatively low melting points (105 °C and 121 °C for 1 and 2 respectively). The structure and thermal properties (thermogravimetry data) of β-ketohydrazonate complexes [Ir(cod)(L)] are compared with those of the related compounds containing β-diketonata and β-ketoiminate ligands.

AB - Within the search for novel promising volatile precursors for the atomic layer deposition new mixed-ligand complexes of iridium(I) with β-ketohydrazones are obtained: [Ir(cod)(dmht)] 1 and [Ir(cod)(dmha)] 2 (cod = cyclooctadiene-1,5, dmht = CF3C(O)CHC(NN(CH3)2)CH3, dmha = CH3C(O)CHC(NN(CH3)2)CH3). The compounds are characterized by the elemental analysis, IR and NMR spectroscopy, and their structures are determined by single crystal X-ray diffraction. In the complex molecules there is a distorted square coordination core IrNOC2′ (C′ is the center of the C=C bond in the cod ligand). The Ir-O, Ir-N bond lengths and Ir-C′ distances are in narrow ranges of 2.027(5)–2.039(3) Å, 2.046(6)–2.074(3) Å, and 1.982(5)–2.017(3) Å respectively. The crystal packing of 1 is of the layered type. Weak pair interactions γC-H…F are observed between the layers. The molecules of 2 form columns packed in the square motif. Shortened intermolecular contacts are not revealed in this structure. The shortest Ir…Ir distances are 5.357 A and 6.420 A in 1 and 2 structures respectively. The synthesized complexes are capable of a quantitative transition to the vapor phase (100–120 °C, 0.05 Torr) and are characterized by relatively low melting points (105 °C and 121 °C for 1 and 2 respectively). The structure and thermal properties (thermogravimetry data) of β-ketohydrazonate complexes [Ir(cod)(L)] are compared with those of the related compounds containing β-diketonata and β-ketoiminate ligands.

KW - iridium(I)

KW - single crystal X-ray diffraction analysis

KW - thermal analysis

KW - volatile precursor

KW - β-ketohydrazonate

KW - THIN-FILMS

KW - OXIDE

KW - beta-ketohydrazonate

KW - CHEMISTRY

KW - WATER OXIDATION

KW - ATOMIC LAYER DEPOSITION

KW - PRECURSORS

UR - http://www.scopus.com/inward/record.url?scp=85087940754&partnerID=8YFLogxK

U2 - 10.1134/S0022476620010126

DO - 10.1134/S0022476620010126

M3 - Article

AN - SCOPUS:85087940754

VL - 61

SP - 109

EP - 118

JO - Journal of Structural Chemistry

JF - Journal of Structural Chemistry

SN - 0022-4766

IS - 1

ER -