Synthesis of binuclear complexes bound in an enlarged tetraphosphamacrocycle: two diphosphine metal units linked in front-to-front style.
A large-hole tetraphosphamacrocycle 2, with four phosphorus centers separated at the corners of a 3.7 A wide and 9.7 A long rectangle, was synthesized by a stepwise cyclization reaction between PCl-bridged [1.1]ferrocenophane and bisphenol A in a 2:2 ratio. The macrocycle 2 could incorporate two Ag(+) or Pt(0) fragments in the hole to provide binuclear complexes, which were identified as mu-2-[Ag(NCMe)(2)](2)(BF(4))(2) (3) and mu-2-[Pt(PhCCPh)](2) (5), respectively, using X-ray and spectroscopic analysis. The X-ray structure of 3 demonstrates that the macrocycle 2 serves as a framework in which two diphosphine silver units are aligned in a front-to-front style, while that of 5 indicates that 2 can also bind two bulky Pt(PhCCPh) fragments by the flexible change of its conformation.
Mizuta
Tsutomu
T
Department of Chemistry, Graduate School of Science, Hiroshima University, Kagamiyama 1-3-1, Higashi-Hiroshima, Hiroshima 739-8526, Japan. mizuta@sci.hiroshima-u.ac.jp
Inami
Yuta
Y
Kubo
Kazuyuki
K
Miyoshi
Katsuhiko
K