High-nuclearity close-packed palladium-nickel carbonyl phosphine clusters: heteropalladium.

[Pd(16)Ni(4)(CO)(22)(PPh(3))(4)](2)(-) (1) and [Pd(33)Ni(9)(CO)(41)(PPh(3))(6)](4)(-) (2) were obtained as the two major products from the reduction of PdCl(2)(PPh(3))(2) with [Ni(6)(CO)(12)](2)(-). Their crystal structures as [PPh(4)](+) salts were unambiguously determined from CCD X-ray crystallographic analyses; the resulting stoichiometries were ascertained from elemental analyses. Infrared, multinuclear (1)H, (31)P[(1)H] NMR, UV-vis, CV, variable-temperature magnetic susceptibility, and ESI FT/ICR mass spectrometric measurements were performed. The Pd(16)Ni(4) core of 1 ideally conforms to a ccp nu(3) tetrahedron of pseudo-T(d)() (4 3m) symmetry. Its geometry normal to each tetrahedral Pd(7)Ni(3) face (i.e., along each of the four 3-fold axes) may be viewed as a four-layer stacking of 20 metal atoms in a ccp [a(Ni(1)) b(Pd(3)) c(Pd(6)) a(Pd(7)Ni(3))] sequence. A comparative analysis of the different ligand connectivities about the analogous metal-core geometries in 1 and the previously reported [Os(20)(CO)(40)](2)(-) has stereochemical implications pertaining to the different possible modes of carbon monoxide attachment to ccp metal(111) surfaces. The unique geometry of the Pd(33)Ni(9) core of 2, which has pseudo-D(3)(h)() (6 2m) symmetry, consists of five equilateral triangular layers that are stacked in a hcp [a(Pd(7)Ni(3)) b(Pd(6)) a(Pd(7)Ni(3)) b(Pd(6)) a(Pd(7)Ni(3))] sequence. Variable-temperature magnetic susceptibility measurements indicated both 1 and 2 to be diamagnetic over the entire temperature range from 5.0 to 300 K. Neutral Pd(12)(CO)(12)(PPh(3))(6) (3) and [Pd(29)(CO)(28)(PPh(3))(7)](2)(-) (4) as the [PPh(4)](+) salt were obtained as minor decomposition products from protonation reactions of 1 and 2, respectively, with acetic acid. Compound 3 of pseudo-D(3)(d)() (3 2/m) symmetry represents the second highly deformed hexacapped octahedral member of the previously established homopalladium family of clusters containing uncapped, monocapped, bicapped, and tetracapped Pd(6) octahedra. The unprecedented centered 28-atom polyhedron for the Pd(29) core of 4 of pseudo-C(3)(v)() (3m) symmetry may be described as a four-layer stacking of 29 metal atoms in a mixed hcp/ccp [a(Pd(1)) b(Pd(3)) a(Pd(10)) c(Pd(15))] sequence.

Effect of reproductive status on feline renal size.

Renal length and width dimensions were determined from survey radiography and excretory urography in 28 cats of various sex and reproductive status. Renal dimensions were expressed as a ratio to the length of the second lumbar vertebra. Renal dimensions were not significantly different when males were compared to females. However, significant differences in renal dimensions between intact and neutered cats were identified. Renal length ratios for neutered cats were: left kidney 2.22 +/- 0.14 (mean +/- standard deviation), right kidney 2.29 +/- 0.14. In intact cats, renal length ratios were: left kidney 2.60 +/- 0.19, right kidney 2.65 +/- 0.24. The mean renal length ratios for neutered cats was smaller than previously reported normal values. Thus, reproductive status should be considered when evaluating feline kidneys for alterations in size. Based on this study, normal feline renal length ratios range from 1.9 to 2.6 for neutered cats and 2.1 to 3.2 for intact cats.

Effects of prepubertal gonadectomy on physical and behavioral development in cats.

OBJECTIVE: To determine the effect of prepubertal gonadectomy on physical and behavioral development in cats. DESIGN: Prospective controlled study of kittens randomly assigned to 3 treatment groups: group 1, neutered at 7 weeks of age; group 2, neutered at 7 months of age; and group 3, sexually intact controls. ANIMALS: 31 clinically normal male and female kittens. PROCEDURE: Age at distal radial physeal closure and mature radius length were determined radiographically. Six behavioral characteristics were recorded monthly. At 1 year of age, body weight was recorded and thickness of the falciform ligament was measured from a lateral abdominal radiographic view. Secondary sex characteristics were also examined at 1 year of age. RESULTS: There were no differences between group-1 and group-2 cats for any of the study variables. Sexually intact cats (group 3) weighted significantly less than group-2 cats and had less falciform fat and earlier distal radial physeal closure than cats of both neutered groups. Group-3 cats manifested greater intraspecies aggression, less affection, and greater development of secondary sex characteristics than neutered cats. CLINICAL IMPLICATIONS: Neutering cats at 7 weeks of age had similar effects on physical and behavioral development, compared with neutering at the more traditional age of 7 months. These data lend support to the concept of prepubertal gonadectomy, already performed by many animal shelters/humane organizations, as a method of enhancing the effectiveness of pet population control programs.

Gonadectomy in immature dogs: effects on skeletal, physical, and behavioral development.

In a 15-month study, the effects of prepubertal gonadectomy on skeletal growth, weight gain, food intake, body fat, secondary sex characteristics, and behavioral development were investigated in 32 mixed-breed dogs. Male and female pups from 5 litters were randomly allotted to 3 groups: group I, neuter at 7 weeks (n = 14); group II, neuter at 7 months (n = 8); and group III, sexually intact dogs (n = 10). Growth plate closure was delayed (group I vs group III; P less than 0.000001; group II vs group III, P less than 0.000001) in all neutered dogs, as compared with sexually intact dogs. Growth plate closure was delayed longer (group I vs group II, P less than 0.000045) in dogs neutered at 7 weeks old, compared with dogs neutered at 7 months old. The rate of growth was unaffected by gonadectomy, but the extended growth period resulted in greater final radial/ulnar length in all male dogs and bitches neutered at 7 weeks. Gonadectomy did not influence food intake, weight gain, or back-fat depth. Penile development was immature in the adult group-I males (mean +/- SEM diameter of pars glandis = 11.1 +/- 1.0 mm), compared with adult group-II (16.3 +/- 0.5 mm) and group-III (21.0 +/- 2.2 mm) males. Subjectively, the prepuce and os penis of the group-I males were immature, compared with those of group-II and group-III males. Vulvar development in group-I and group-II bitches was less mature than vulvar development in the sexually intact bitches. Of 7 behavioral characteristics assessed, only general activity and excitability rated differently among treatment groups. All neutered dogs were judged to be more active (group I, P less than 0.004) than sexually intact dogs. Group-I males were judged to be more excitable (P less than 0.02) than group-III males. It was concluded that with respect to skeletal, physical, and behavioral development, the effect of neutering pups at 7 weeks old was similar to that of neutering pups at 7 months old.