CARBONYL MANGANESE CLUSTERS WITH GALLIUM, INDIUM AND THALLIUM

The reaction of AlCl3 With [As(C6H5)4]2[mu-H)Mn3(mu-CO)2(CO)10] (1) gi ves the carbonylmanganese clusters [(mu-H)Mn5(CO)17]2- (A2) and [(mu-H )3Mn3(CO)12] (3). Reaction of GaCl3 with K3[Mn3(mu-CO)2(CO)10] (4) yie lds the cluster dianions [Mn3(CO)12{mu-GaCl2}]2-(A5) and [Mn3(CO)12{mu -GaCl(OH)}]2- (A6). InCl3 reacts with 4 to give the anionic complexes [Mn2(CO)8{mu-InClMn(CO)5}2]2-(A7), [In{Mn3(CO)12}2]3- (A8) and [(mu5-1 n){Mn(CO)4}5]2- (A9). In A8 the indium atom functions as a spirocenter ; A9 has an idealised pentagonal-planar structure. Reaction of Tl(CH3C OO)3 with 1 affords the Tl-Mn clusters [(mu-H)Mn3(CO)12{mu-TlMn(CO)5}] (10) and [Tl2{mu-Mn(CO)4}{(mu-H)Mn3(CO)12}2]- (A11); in A11 a Tl-Tl b ond is observed. X-ray diffraction studies of the tetraphenylarsonium salts 5 and 11 of the cluster anions A5 and All and of 10 are describe d.