Infrared Spectroscopic Study of the Matrix-Isolated Complexes of TiCl₄ with PH₃ and AsH₃

Abstract

The 1:1 complexes of TiCl4 with PH3 and AsH3 have been characterized in argon matrices. Intense spectral features in the 400−500 cm-1 region were assigned to Ti−Cl antisymmetric stretching modes in each complex, shifted from the parent mode near 500 cm-1, while the bending modes of coordinated PH3 and AsH3 shifted 15−70 cm-1. The Ti−Cl stretching modes of the complexes shifted with different bases; these shifts correlate with the intrinsic basicity of each base.

Reactions of Aluminum, Gallium, and Indium (M) Atoms with Phosphine: Generation and Characterization of the Species M·PH3, HMPH2, and H2MPH

“…The ν sym (P−H) and δ sym (PH 3 ) frequencies determined here are comparable with those displayed by PH 3 in transition metal complexes. Thus, ν(P−H) modes with frequencies of 2250, 2270, and 2383/2393 cm -1 have been identified for Cu(PH 3 ) n ( n = 1−3), Ni(PH 3 ) 4 , , and H 3 P·TiCl 4 , respectively; δ sym (PH 3 ) for the same species is reported to occur at 958−970, 998, and 967 cm -1 .…”

“…Matrix-isolation experiments have already contributed notably to the study of highly reactive phosphine derivatives. − For example, insertion reactions of the main group atoms O and S into a P−H bond of PH 3 have been observed in this way to yield the products HOPH 2 3,4 and HSPH 2 , respectively. Complexes of PH 3 with transition metal atoms or compounds have also been characterized. − Cocondensation of Cu atoms with PH 3 in Kr matrices results in the formation of Cu(PH 3 ) n complexes ( n = 1, 2, or 3) 6 identified by IR absorptions at 2250 and 970, 968, and 958 cm -1 . Similar experiments indicate that Ni atoms add PH 3 to give Ni(PH 3 ) or Ni(PH 3 ) 4 in Ar or neat PH 3 matrices, respectively. , The 1:1 complex H 3 P·TiCl 4 has also been characterized in this way …”

“…Complexes of PH 3 with transition metal atoms or compounds have also been characterized. − Cocondensation of Cu atoms with PH 3 in Kr matrices results in the formation of Cu(PH 3 ) n complexes ( n = 1, 2, or 3) 6 identified by IR absorptions at 2250 and 970, 968, and 958 cm -1 . Similar experiments indicate that Ni atoms add PH 3 to give Ni(PH 3 ) or Ni(PH 3 ) 4 in Ar or neat PH 3 matrices, respectively. , The 1:1 complex H 3 P·TiCl 4 has also been characterized in this way …”

2 Matrix isolation

“…With PH 3 and AsH 3 similar 1+1 complexes are also formed. 22 The PH 3 complex shows n asym (Ti-Cl) bands at 434 and 467 cm -1 ; the AsH 3 complex has corresponding bands at 436 and 471 cm -1 . This suggests a similar strength of coordination for the three Lewis bases NH 3 , PH 3 and AsH 3 .…”