The molybdenum iodide cluster anion undecaiodotetramolybdate(2-). A new cluster type structurally related to the octaiodohexamolybdenum(4+) octahedral cluster

Molybdenum Iodides – from Obscurity to Bright Luminescence

“…An oxygen‐centered tetranuclear iodide‐bridged cluster (PPh 4 ) 2 [Mo 4 (µ 4 ‐O)(µ 3 ‐I) 2 (µ 2 ‐I 4 )I 6 ] was obtained in a reaction between Mo(CO) 6 , Bu 4 NI and I 2 in diglyme at 110 °C. The structure of the cluster anion can be derived formal oxidative addition of “O” plus “I” to the Mo 4 core in [Mo 4 (µ 3 ‐I) 2 (µ 2 ‐I) 5 I 4 ] 2– (Figure ) , . This leads to formal oxidation of Mo +2.25 to Mo +3 and is accompanied by opening up the longest Mo–Mo bond between the wing‐tip atoms of the parent “butterfly” structure in order to accommodate the capping O 2– ligand.…”

The First Molybdenum Oxo‐iodide Cluster – [Mo4OI12]2–

“…The structure of the butterfly cluster 1 can be derived from formal oxidative addition of “O” + “I” to the distorted tetrahedral Mo 4 core found in (Ph 4 P) 2 [Mo 4 (μ 3 ‐I) 2 (μ 2 ‐I) 5 I 4 ] ( 2 ), as well as in its Bu 4 N + and Ph 4 As + analogues , . This leads to formal oxidation of Mo +2.25 to Mo +3 , which is accompanied by opening up of one of the Mo–Mo edges [that corresponds to the longest Mo–Mo bond of 3.051(3) Å in 2 ] to accommodate the capping O 2– ligand, and of one of the μ 2 ‐I bridges via insertion of an iodine atom: “Mo 2 (μ 2 ‐I)” + “I” = 2”MoI t ”.…”

Preparation and characterization of dimeric and tetrameric clusters of molybdenum and tungsten

“…Removal of one molybdenum atom leaves a square pyramid of metal atoms of the type found in MOgCl^g " (23). Removal of two adjacent molybdenum atoms leaves a distorted tetrahedron of the type found for " (24). The loss of two apical (trans) metal atoms results in a planar molybdenum cluster not unlike Mo^ClgfPRg)^ (25).…”

“…135 (28) 74 (19) 110 (24) -9 (19) 72 (23) -3 (17) C (1A2) 107 (25) 86 (21) 124 (27) 46 (19) 65 (22) 51 (19) cClBl ) 58 (17) 129 (25) 80 (19) 24 (17) 42 (15) 28 (17) C (1B2) 92 (28) 293 (55) 86 (25) 61 (33) 35 (22) 52 (30) C(lCl) 120 (26) 128 (26) 80 (20) -6 (21) 77 (20) 1 (18) C (1C2) 119 (31) 184 (37) 123 (29) 13 (27) 79 (26) 4 (27) C (2B1) 56 (18) 122 (24) 82 (20) -7 (17) 25 (17) 10 (18) C(2B2) 75 (24) 329 (63) 126 ( …”