Four tellurium atoms are weakly linked into a Te4 square in Ph4Te4I4 (1), which is formed from the reaction of Ph2Te2 with diiodine. This novel structural modification was not previously observed for organoelement–halogen compounds of Group 16. Subsequent reaction of 1 with four equivalents of PPh3 produces the charge‐transfer complex Ph3PTe(Ph)I (2).
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